CN103193913A

CN103193913A - Process for producing broader molecular weight distribution polymers with a reverse comonomer distribution and low levels of long chain branches

Info

Publication number: CN103193913A
Application number: CN2013100601206A
Authority: CN
Inventors: 杨清; M·P·麦克丹尼尔; J·L·马丁; T·R·克莱恩; R·S·穆宁格尔; J·T·拉尼尔; J·S·福多尔; P·J·德洛里耶兹; C·C·佐; D·C·罗尔菲
Original assignee: Chevron Phillips Chemical Co LLC
Current assignee: Chevron Phillips Chemical Co LLC
Priority date: 2008-12-18
Filing date: 2009-12-04
Publication date: 2013-07-10
Anticipated expiration: 2029-12-04
Also published as: CN101747462B; EP2376542B1; CN103193913B; EP2703419A1; CO6390003A2; US8475899B2; CA2973523C; MX2011006571A; HK1145507A1; EP2376542A1; EG26723A; SG172066A1; KR101688242B1; CA2746995C; AU2009336168B2; CN101747462A; KR20110103958A; ES2447377T3; ES2612253T3; CA2973523A1

Abstract

The present invention relates to a process for producing broader molecular weight distribution polymers with a reverse comonomer distribution and low levels of long chain branches. The present invention provides a polymerization process which is conducted by contacting an olefin monomer and at least one olefin comonomer in the presence of hydrogen and a metallocene-based catalyst composition. The polymers produced from the polymerization process are also provided, and these polymers have a reverse comonomer distribution, low levels of long chain branches, and a ratio of Mw/Mn from about 3 to about 6.

Description

Generation has the method than broad molecular weight distribution polymers of anti-copolymerization monomer distribution and low levels of long chain branches

The application divides an application, and the applying date of original application is that December 4, application number in 2009 are that 200910252836.X, denomination of invention are " generation has the method than broad molecular weight distribution polymers of anti-copolymerization monomer distribution and low levels of long chain branches ".

Background of invention

The present invention relates in general to polymerization and process for copolymerization and the polyolefinic field of olefinic polymerization catalysis, catalyst composition and alkene.

Use the various combinations of catalyst system and polymerization process can the production polyolefin homopolymer, copolymer, terpolymer etc.A kind ofly can use the Metallocenyl catalyst system for the production of so polyolefinic method.Generally speaking, metallocene catalyst produces the polyolefine with narrow molecular weight distributions.Though having the polymkeric substance of narrow molecular weight distributions may be favourable in the application of some polymer processing operation and end-use, it may be shortcoming in other side.For example, narrow molecular weight distribution polymer may require to use fluoropolymer additive, with in the operation of some polymer processing, do not having flow instability (flow instabilities) for example under the situation of melt fracture with the productivity processable polymer of expectation.The use of fluoropolymer additive has increased the cost by polymer production finished product object.In other polymer processing operational example such as blown film and blow molding (blow molding), narrow molecular weight distribution polymer with compare than broad molecular weight distribution polymers, stability can reduce usually, causes output or production rate to reduce.

The general polymkeric substance with narrow molecular weight distributions that produces of Metallocenyl catalyst system.Other catalyst system for example chromium or Ziegler-type can produce the wider molecular weight distribution polymkeric substance.Yet when using chromium or Ziegler-type catalyst system, the use of hydrogen makes molecular weight distribution narrow down in olefinic polymerization.

Therefore, in the presence of hydrogen, use the Metallocenyl catalyst system will be conducive to produce than broad molecular weight distribution polymers.Therefore, these purposes just that the present invention relates to.

Summary of the invention

The present invention relates in general to catalyst composition, prepares the method for catalyst composition, uses the method for catalyst composition olefin polymerization, the object that uses the fluoropolymer resin of these catalyst composition productions and use these fluoropolymer resins to produce.According to an aspect of of the present present invention, disclosing can be for the production of the olefine polymerizing process of for example ethylene copolymer.This method comprises:

Catalyst composition is contacted, to produce olefin polymer under polymerizing condition with at least a olefin comonomer with olefinic monomer; Wherein:

Catalyst composition comprises the product of contact of at least a metallocene compound and at least a activator;

Polymerization process carries out in the presence of hydrogen; With

Olefin polymer has from about 3 to about 6 Mw/Mn ratio.

Randomly, in this catalyst composition and polymerization process, can use organo-aluminium compound.At least a metallocene compound is the bridged combined metal compound that has cyclopentadienyl and fluorenyl part simultaneously, and it is represented with following formula:

Wherein:

M ¹Be Ti, Zr or Hf;

X is F independently; Cl; Br; I; Methyl; Phenyl; H; BH ₄OBR ^A ₂Or SO ₃RA, wherein R ^AIt is the alkyl or aryl group with 12 carbon atoms of as many as; Or-oxyl (hydrocarbyloxide) group, hydrocarbon amino (hydrocarbylamino) group or alkyl silyl (hydrocarbylsilyl) group, wherein any can have 20 carbon atoms of as many as;

E is C or Si;

R ¹And R ²Be H or the alkyl or aryl group with 12 carbon atoms of as many as, wherein R independently ¹And R ²In at least one is aromatic yl group;

R ^3AAnd R ^3BBe H or alkyl or the alkyl silyl-group with 20 carbon atoms of as many as independently;

R ⁴It is the alkyl or alkenyl group with 10 carbon atoms of as many as; With

R ^5AAnd R ^5BBe H or the hydrocarbyl group with 12 carbon atoms of as many as independently.

Can use the catalyst composition for olefinic polymerization disclosed herein and method to produce olefin polymer.For example, ethene polymers of the present invention can characterize with following polymer property:

From about melt index of 0.1 to about 100g/10min;

From about 3 to about 6 Mw/Mn ratio;

Anti-copolymerization monomer distribution;

Per 1000 total carbon atoms less than about 0.05 long chain branches (long chain branches) (LCB); With

In ATREF test below the temperature of 40 ° of C, by weight less than about 5% polymkeric substance by wash-out.

The accompanying drawing summary

Fig. 1 is illustrated in the metallocene compound MET1, the MET2 that use in following examples and the structure of MET3.

Fig. 2 is illustrated in the definition of D90 and D10 on the molecular weight distribution curve.

Fig. 3 provides the graph of molecular weight distribution of the polymkeric substance of embodiment 1-2.

Fig. 4 provides the graph of molecular weight distribution of the polymkeric substance of embodiment 3-7.

Fig. 5 provides the graph of molecular weight distribution of the polymkeric substance of embodiment 8-14.

Fig. 6 provides the short chain branch distribution plan of the polymkeric substance of embodiment 9 and embodiment 12.

Fig. 7 provides the graph of molecular weight distribution of the polymkeric substance of embodiment 15-20.

Fig. 8 provides the graph of molecular weight distribution of the polymkeric substance of embodiment 15 and embodiment 21-25.

Fig. 9 provides the short chain branch distribution plan of the polymkeric substance of embodiment 20-25.

Figure 10 provides the short chain branch distribution plan of the polymkeric substance of embodiment 26-28.

Figure 11 provides the zero shear viscosity of polymkeric substance of embodiment 3-6,8-11 and 17-27 to the figure of weight-average molecular weight, specifically, and log (η ₀) to log (Mw).

Figure 12 provides the figure of ATREF profile (profiles) of the polymkeric substance of embodiment 20-26.

Figure 13 provides the graph of molecular weight distribution of the polymkeric substance of embodiment 29-32.

Definition and abbreviation

In order more clearly to define term used herein, provide following definition and abbreviation.Any definition that provides with regard to any document of incorporating this paper by reference into or usage are as the criterion with definition provided herein or usage with regard to definition provided herein or usage are conflicted.

ATREF – analysis temperature rising elution fractionation (Analytical temperature rising elution fractionation).

The molecular weight of D10 – when wherein 10% polymkeric substance has higher molecular weight by weight.

The molecular weight of D90 – when wherein 90% polymkeric substance has higher molecular weight by weight.

HLMI – high load melt index.

LCB – long chain branches.

M – molecular weight.

Me – methyl.

MI – melt index.

Mn – number-average molecular weight.

Mw – weight-average molecular weight.

Mw/Mn – ratio is the measurement of molecular weight distribution; Be also referred to as polydispersity index.

η ₀The – zero shear viscosity.

Ph – phenyl.

SCB-short chain branch.

SCBD-short chain branch distributes or short-chain branched distribution.

The t-Bu-tertiary butyl (Tert-butyl) or the tertiary butyl (t-butyl).

TC – total carbon or total carbon atom.

The TIBA triisobutyl aluminium.

TNBA-three n-butylaluminum.

In term " polymer " used herein " totally comprise olefin homo, copolymer, terpolymer etc.Though term polymer comprises homopolymer, the present invention relates generally to the polymkeric substance that comes from olefinic monomer and at least a olefin comonomer.Therefore, copolymer comes from olefinic monomer and a kind of olefin comonomer, and terpolymer comes from olefinic monomer and two kinds of olefin comonomers.Therefore, " polymkeric substance " comprises the copolymer that comes from any olefinic monomer disclosed herein and comonomer (one or more), terpolymer etc.Similarly, ethene polymers can comprise ethene copolymer, ethylene-dien terpolymer etc.As an example, alkene copolymer such as ethene copolymer can come from ethene and comonomer such as 1-butylene, 1-hexene or 1-octene.If monomer and comonomer are respectively ethene and 1-hexene, the polymkeric substance of generation can be classified as ethene/1-hexene copolymer.

In a similar manner, the scope of term " polymerization " comprises homopolymerization, binary homopolymerization, ternary homopolymerization etc.Therefore, the binary copolymerization process can comprise and makes a kind of olefinic monomer (for example ethene) contact to produce copolymer with a kind of olefin comonomer (for example 1-hexene).

Hydrogen in the disclosure can refer to the hydrogen molecule (H that uses in polymerization process ₂) or may reside in hydrogen atom on formula (I) the bridged combined metal compound.When being used to indicate hydrogen atom, hydrogen can be shown as " H ", and if purpose is to be disclosed in to use hydrogen in the polymerization process, it can be called " hydrogen " simply.

Generally use term " promotor " to refer to constitute the organo-aluminium compound of a kind of composition of catalyst composition herein.In addition, " promotor " can refer to other composition of catalyst composition, includes but not limited to as at aikyiaiurnirsoxan beta disclosed herein, organic boron or organic borate (organoborate) and ionizing ionic compound.Use term " promotor " and no matter the actual functional capability of compound or any chemism that compound can work how.In one aspect of the invention, use " promotor " so that this composition of catalyst composition and the difference of metallocene composition are come.

This paper uses term " fluorine organoboron compound " under its its ordinary meaning, refer to BY ₃The neutral compound of form.Term " fluorine organic boronic salt compound " also has its common implication, refers to [positively charged ion] ⁺[BY ₄] ^-The single anion salt of the fluorine organoboron compound of form, wherein Y represents the organic group fluoridized.The material of these types usually and generally is called " organic boron or organic boronic salt compound ".

This paper uses term " product of contact " to describe composition wherein with any order, the composition that contacts with random time length by any way.For example, composition can or mix contact by blending.Further, the contact of any composition can take place in the existence of any other composition of composition described herein or not.Can be in conjunction with other material or composition by any appropriate means.Further, term " product of contact " comprises mixture, admixture, solution, slurry, reaction product etc. or its combination.Though " product of contact " can comprise reaction product, do not require each composition interreaction.

This paper use term " preceding contact " (precontacted) mixture first mixture of the catalyst component of first period of contact is described, this first mixture is used to form " back contact (postcontacted) " mixture or second mixture of the catalyst component of second period of contact then.Usually, before the contact compound mixture of metallocene compound (or multiple metallocene compound), olefinic monomer and organo-aluminium compound (or multiple organo-aluminium compound) is described, this mixture and activator (one or more) and/or activator-carrier (one or more) and the other organo-aluminium compound (one or more) chosen wantonly contact then.Therefore, the composition that is used for contacting with each other but contacted is described in preceding contact before the composition of contact second, back contact mixture.Therefore, the present invention sometimes can distinguish for the preparation of the composition of preceding contact mixture and this composition after preparing this mixture.For example, according to this description, in case preceding contact organo-aluminium compound contacts with olefinic monomer with metallocene, preceding contact organo-aluminium compound may react, and forms at least a chemical compound, chemical formula or the structure that is different from for the preparation of unique organo-aluminium compound of preceding contact mixture.In this case, preceding contact organo-aluminium compound or composition are described to comprise the organo-aluminium compound for the preparation of this preceding contact mixture.

Alternatively, preceding contact mixture can be described the mixture of metallocene compound (one or more) and organo-aluminium compound (one or more), and this mixture is contacted with activator (one or more) and/or activator-carrier (one or more).Contact mixture also can be described the mixture of metallocene compound (one or more), olefinic monomer and activator (one or more) and/or activator-carrier (one or more) before this, and this mixture contacts with organoaluminum cocatalyst compound or multiple organoaluminum cocatalyst compound then.

Similarly, this paper uses term " back contact " mixture to describe second mixture of the catalyst component of second period of contact, and its a kind of component is " preceding contact " mixture or first mixture of the catalyst component of first period of contact.Typically, term used herein " back contact " mixture is described the mixture of metallocene compound (one or more), olefinic monomer, organo-aluminium compound (one or more) and activator (one or more) and/or activator-carrier (one or more), the preceding contact mixture of this mixture by these compositions of a part with increase any other composition of forming the back contact mixture and contact and form.Usually, activator and/or activator carrier are chemically treated solid oxidation compounds.For example, increase the other composition form the back contact mixture and can be chemically treated solid oxidation compounds (or number of chemical handle solid oxidation compounds), and randomly can comprise with for the preparation of the identical or different organo-aluminium compound of the organo-aluminium compound of contact mixture before as described herein.Therefore, the present invention also can distinguish sometimes for the preparation of the composition of back contact mixture and this composition after this mixture has prepared.

Term " metallocene " is described and is comprised at least a η as used herein ³To η ⁵The compound of-loop chain diene fundamental mode part, wherein η ³To η ⁵-loop chain dialkylene partly comprises cyclopentadienyl ligands, indenyl ligands, fluorenyl ligand etc., comprises in these any fractional saturation or derivative or the analogue of replacement.Therefore possible substituting group on these parts comprises hydrogen, describes " its substitutive derivative " in the present invention and comprises the part of fractional saturation such as tetrahydro indenyl, tetrahydrofluorenyl, octahydrofluorenyl, fractional saturation indenyl, fractional saturation fluorenyl, the fractional saturation indenyl of replacement, the fractional saturation fluorenyl of replacement etc.For example, the compound that is comprised by formula (I) is the bridged combined metal compound that has cyclopentadienyl and fluorenyl part simultaneously.In some cases, metallocene compound is called " catalyzer " simply, and similarly term " promotor " is used in reference to for example organo-aluminium compound at this paper.

Term " catalyst composition ", " catalyst mixture ", " catalyst system " etc. do not rely on the character at actual product that contact or reaction by mix ingredients obtain, active catalytic position or promotor, bridged combined metal compound, any olefinic monomer or activator or or course of promoting agent-carrier for the preparation of preceding contact mixture after in conjunction with these compositions.Therefore, term " catalyst composition ", " catalyst mixture ", " catalyst system " etc. can comprise heterogeneous compositions and homogeneous composition simultaneously.

This paper uses solid, the inorganic oxide of the relative high porosities of expression such as term " chemical treatment soild oxide ", " soild oxide activator-carrier " " solid oxidation compounds of processing ", it shows Lewis acid or Bronsted acidity matter, and it becomes divisional processing with the electrophilic that typically is negatively charged ion and is calcined.The electrophilic composition typically is electrophilic negative ion source compound.Therefore, chemical treatment solid oxidation compounds comprises the calcining product of contact of at least a solid oxidation compounds and at least a electrophilic negative ion source compound.Typically, the chemical treatment soild oxide comprises at least a ionization, acidic solid oxide compound.Term " carrier " and " activator-carrier " are not inertia for these compositions of expression, and these compositions should not be interpreted as the inert fraction of catalyst composition.Activator-carrier of the present invention can be chemically treated soild oxide.

Can use in practice or test the present invention though be similar to or be equal to any method described herein, device and material, typical method, device and material are described at this paper.

All publications mentioned in this article and patent are incorporated this paper by reference into, are used for concept and methodology that description and open for example publication are described, and they can be used together with the invention of this description.The publication of discussing in providing in full is only because they are open before the application's the applying date.This paper will be interpreted as admitting that without any thing the inventor does not have right to take the lead in this open owing to what before invented.

Also comprise for any specific compound disclosed herein, any structure that provides and can result from one group of specific substituent all conformers, positional isomers (regioisomers) and steric isomer.No matter structure comprises that also all enantiomers, diastereomer and other are with the optical isomer of enantiomer or racemization form and the mixture of steric isomer, as recognized by those skilled in the art.

The applicant discloses the scope of a few types in the present invention.These include but not limited to scope, melt index range, density range of scope, the molecular weight of scope, the temperature of scope, the mol ratio of scope, the weight ratio of atomic quantity etc.During the scope of or claimed any kind open as the applicant; the applicant is intended that individually each possible numerical value open or that claimed this scope can reasonably comprise, comprises the end points of scope and any subrange that comprises therein and the combination of subrange.For example, when the open or claimed chemical part with certain carbonatoms of applicant, being intended that of applicant is individually open or claimedly disclose each possible quantity that this consistent scope can comprise with this paper.For example, as used herein, part is the disclosing to refer to be independently selected from and have 1 of hydrocarbyl group with 1 to 20 carbon atom, 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18, the hydrocarbyl group of 19 or 20 carbon atoms and any scope between these two numerical value (for example, hydrocarbyl group with 3 to 12 carbon atoms) part, and also comprise any combination (hydrocarbyl group and the hydrocarbyl group with 8 to 12 carbon atoms that for example, have 1 to 4 carbon atom) of scope between these two numerical value.

Similarly, be another representational example below, its Mw at the polymkeric substance that provides in an aspect of of the present present invention (weight-average molecular weight).For the Mw of open polymkeric substance from about 20,000 to about 250, the scope of 000g/mol, the applicant is intended to state that this Mw can be selected from about 20,000, about 30,000, about 40,000, about 50,000, about 60,000, about 70,000, about 80,000, about 90,000, about 100,000, about 110,000, about 120,000, about 130,000, about 140,000, about 150,000, about 160,000, about 170,000, about 180,000, about 190,000, about 200,000, about 210,000, about 220,000, about 230,000, about 240,000, or about 250,000g/mol.In addition, this Mw can in any scope of about 20,000 to about 250,000 (for example, this Mw from about 70,000 in about 150,000 scope), and this also comprises any combination of scope between about 20,000 to about 250,000.Similarly, all other scopes disclosed herein should be explained in the mode that is similar to these two examples.

The applicant keeps restriction (proviso out) or gets rid of any any such group indivedual member right; the composition that comprises interior any subrange of this group or subrange; it can be according to scope or claimed with any similar fashion; if because any reason applicant selects claimed less than disclosed FR words; for example, the documents in order to consider that the applicant may not recognize when the submit applications.Further; the applicant keeps restriction or gets rid of any other substituting group, analogue, compound, part, structure or its group, claimed group arbitrary member's right; if because any reason applicant selects claimed less than disclosed FR words; for example, the documents in order to consider that the applicant can not recognize when the submit applications.

Though described composition and method according to " comprising " various compositions or step, composition and method also can " be made up of various compositions or step " or " being made up of various compositions or step " substantially.

Detailed Description Of The Invention

The present invention relates in general to catalyst composition, the method for the preparation of catalyst composition, the method for use catalyst composition polymkeric substance alkene, the object that uses the fluoropolymer resin of these catalyst composition productions and use these fluoropolymer resins to produce.On the one hand, the present invention relates to olefine polymerizing process, described method comprises:

Polymerization process carries out in the presence of hydrogen; With

Olefin polymer has from about 3 to about 6 Mw/Mn ratio.

Alkene copolymer, terpolymer etc. can use the catalyst composition for olefinic polymerization disclosed herein and method to produce.For example, ethene polymers of the present invention can characterize by following polymer property:

From about melt index of 0.1 to about 100g/10min;

From about 3 to about 6 Mw/Mn ratio;

Anti-copolymerization monomer distribution;

Per 1000 total carbon atoms are less than about 0.05LCB; With

Metallocene compound

The present invention uses the bridged combined metal compound that has cyclopentadienyl and fluorenyl part simultaneously.In one aspect of the invention, this bridged combined metal compound has following formula:

Wherein:

M ¹Be Ti, Zr or Hf;

X is F independently; Cl; Br; I; Methyl; Phenyl; H; BH ₄OBR ^A ₂Or SO ₃R ^A, R wherein ^AIt is the alkyl or aryl group with 12 carbon atoms of as many as; Or-oxyl group, hydrocarbon amino group or alkyl silyl-group, wherein any can have 20 carbon atoms of as many as;

E is C or Si;

R ⁴It is the alkyl or alkenyl group with 10 carbon atoms of as many as; With

Above formula (I) purpose is not to show stereochemistry or the isomery placement (for example, this formula does not plan to show suitable or trans isomer or R or S diastereomer) with different piece, though these compounds are considered by this formula and comprised.

Metal M in the formula (I) ¹Be Ti, Zr or Hf.Each X is F independently in the formula (I); Cl; Br; I; Methyl; Phenyl; H; BH ⁴OBR ^A ₂Or SO ₃R ^A, R wherein ^AIt is the alkyl or aryl group with 12 carbon atoms of as many as; Or-oxyl group, hydrocarbon amino group or alkyl silyl-group, wherein any can have 20 carbon atoms of as many as.Unless certain illustrated is arranged in addition, open alkyl group is intended to comprise all constitutional isomers to certain portions---linearity or side chain; For example, all enantiomers and all diastereomers are included in this range of definition.As an example, unless certain illustrated is arranged in addition, the term propyl group is intended to comprise n-propyl and sec.-propyl, and the term butyl is intended to comprise normal-butyl, isobutyl-, the tertiary butyl, sec-butyl etc.For example, the non-limitative example of octyl group isomer comprises 2-ethylhexyl and new octyl group.Example with suitable alkyl of 12 carbon atoms of as many as, it can be used as OBR ^A ₂Or SO ₃R ^AIn R ^A, include but not limited to methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl or decyl etc.

Among the present invention, aromatic yl group with 12 carbon atoms of as many as comprises aryl and aromatic alkyl group simultaneously, and the naphthyl that replaces of these phenyl, naphthyl, alkyl that include but not limited to that phenyl, alkyl replace, the alkyl that phenyl replaces, the alkyl of naphthyl substituted etc.Therefore, the non-limitative example of these aryl moieties, it can be used as OBR ^A ₂Or SO ₃R ^AIn R ^A, comprise phenyl, benzyl, tolyl, 3,5-dimethylphenyl, trimethylphenyl, styroyl, hydrocinnamyl, phenyl butyl, propyl group-2-styroyl etc.Unless certain illustrated is arranged in addition, any aromatic yl group used herein such as aromatic alkyl group are intended to comprise all positional isomerss; For example, the term tolyl is intended to comprise any possible substituting group position, namely adjacent, or right.

This paper uses term " alkyl " to refer to the hydrocarbon free radical, and include but not limited to aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl group, loop chain dialkylene, alkynyl, aralkyl, arylalkenyl, sweet-smelling alkynyl etc., and comprise derivative its all replacements, unsubstituted, side chain, linear or that heteroatoms replaces.Unless certain illustrated is arranged in addition, hydrocarbyl group of the present invention typically comprises about 20 carbon atoms of as many as.On the one hand, hydrocarbyl group can have 12 carbon atoms of as many as in addition, for example, and 8 carbon atoms of as many as or 6 carbon atoms of as many as.Therefore, generally use the-oxyl group to comprise alcoxyl (alkoxide) group and aryloxy group simultaneously, and these groups can comprise about 20 carbon atoms of as many as.The phenoxy group that the illustrative of alkoxy grp and aryloxy group (that is-oxyl group) and non-limitative example comprise methoxyl group, oxyethyl group, propoxy-, butoxy, phenoxy group, replacement etc.Similarly, generally use term hydrocarbon amino group totally to refer to alkylamino, arylamino, dialkyl amido and ammonia diaryl base group.Unless certain illustrated is arranged in addition, hydrocarbon amino group of the present invention comprises about 20 carbon atoms of as many as.The alkyl silyl-group includes but not limited to alkyl silyl-group, aryl silyl-group, aralkyl silyl-group etc., and they have 20 carbon atoms of as many as.For example, the alkyl silyl-group can comprise trimethyl silyl and phenyl octyl group silyl-group.These-oxyls, hydrocarbon amino and alkyl silyl-group can have 12 carbon atoms of as many as, or alternatively, 8 carbon atoms of as many as in other side of the present invention.

According to an aspect of of the present present invention, each X in the formula (I) is independently selected from F, Cl, Br, I, methyl, phenyl, H, BH ₄, methoxyl group, oxyethyl group, propoxy-, phenoxy group and trimethyl silyl.On the one hand, at least one X is Cl, methyl, phenyl or H in addition.Also in addition on the one hand, each X is Cl or methyl independently.

Bridging atom E in the formula (I) is C or Si, and R ¹And R ²Be H or the alkyl or aryl group with 12 carbon atoms of as many as independently.Yet, R ¹And R ²In at least one be aromatic yl group.Independently, R ¹And R ²Can be any of the alkyl or aryl group with 12 carbon atoms of as many as discussed above.For example, R ¹And R ²Can be independently selected from H, methyl, ethyl, propyl group, butyl, phenyl, benzyl and tolyl.According to an aspect of of the present present invention, R ¹And R ²It is the aromatic yl group with 12 carbon atoms of as many as.Alternatively, R ¹And R ²Can be methyl or phenyl, wherein R ¹And R ²In at least one be phenyl.

In the formula (I), R ^3AAnd R ^3BBe H or alkyl or the alkyl silyl-group with 20 carbon atoms of as many as independently.R ^3AAnd R ^3BCan be the have alkyl of 20 carbon atoms of as many as or any in the alkyl silyl-group discussed above.R ^3AAnd R ^3BCan be independently, for example, H, methyl, ethyl, propyl group, butyl, phenyl, hexyl, allyl group, benzyl, phenyl or trimethyl silyl etc.In addition on the one hand, R ^3AAnd R ^3BBe H or methyl independently.R in the formula (I) ⁴It is the alkyl or alkenyl group with 10 carbon atoms of as many as.R ⁴Suitable alkyl and thiazolinyl select to include but not limited to methyl, ethyl, propyl group, butyl, amyl group, hexyl, vinyl, propenyl, butenyl, pentenyl, hexenyl etc.C ₂-C ₁₀Alkenyl group is not restricted to the regioselectivity (regiochemistry) of alkene functional group, and it can be linearity or side chain, discusses with respect to alkyl group as above.Some aspects, ethylene linkage are away from cyclopentadienyl ligands, and therefore can be described as side (pendant) alkenyl group.For example, in one aspect of the invention, R ⁴It is the linear alkenyl group with 6 carbon atoms of as many as.In addition on the one hand, R ⁴Be vinyl, propenyl, butenyl, pentenyl or hexenyl.Therefore, R ⁴Can be for example allyl group, butylene-3-base, amylene-4-base, hexene-5-base, 3-methyl butene-3-base, 4-methylpentene-4-base etc. of alkenyl group.

R in the formula (I) ^5AAnd R ^5BBe H or the hydrocarbyl group with 12 carbon atoms of as many as independently.R ^5AAnd R ^5BCan be any that has as discussed above in the hydrocarbyl group of 12 carbon atoms of as many as.R ^5AAnd R ^5BCan be independently, for example, H, methyl, ethyl, propyl group, butyl, amyl group, hexyl, allyl group, benzyl or phenyl etc.On the other hand, R ^5AAnd R ^5BBe H or the tertiary butyl independently.Also in addition on the one hand, R ^5AAnd R ^5BIt all is the tertiary butyl.

According to an aspect of of the present present invention, M ¹Be Zr or the Hf in the formula (I); Each X is Cl, methyl or phenyl independently; E is C; R ¹And R ²Be methyl, ethyl, phenyl or benzyl, wherein R independently ¹And R ²In at least one be phenyl; R ^3AAnd R ^3BBe H, methyl, ethyl or trimethyl silyl independently; R ⁴Be vinyl, propenyl, butenyl or pentenyl; And R ^5AAnd R ^5BBe H, methyl, ethyl, propyl group or the tertiary butyl independently.

The illustrative of bridged combined metal compound of the present invention and non-limitative example include, but are not limited to following compound:

Deng.

The structure of the metallocene compound that Fig. 1 explanation is used in following examples.Metallocene among Fig. 1 " MET1 " expression bridged combined metal compound of the present invention.Metallocene " MET2 " is the bridged combined metal compound of comparison.Metallocene " MET3 " is the not bridged combined metal compound of comparison.

A plurality of methods of the bridged combined metal compound that preparation can be used have in the present invention been reported.For example, United States Patent (USP) 5,191,132,5,210,352,5,399,636,5,401,817,5,420,320,5,436,305,5,451,649,5,498,581,5,571,880,5,631,203,5,631,335,5,654,454,5,705,579,6,187,880 and 6,509,427 have described these methods.Other method of the bridged combined metal compound that preparation can be used in the present invention can find in reference, for example: A.Alt, H.G.J.Mol.CatalA.2001,165,23; Kajigaeshi, S.; Kadowaki, T.; Nishida, A.; Fujisaki, S.Bulletin of the Chemical Society of Japan, 1986,59,97; Alt, H.G.; Jung, M.; Kehr, G.J.Organomet.Chem.1998,562,153-181; Alt, H.G.; Jung, M.J.Organomet.Chem.1998,568,87-112; Jung, M., Doctoral Dissertation, University of Bayreuth, Bayreuth, Germany, 1997; Piefer, B., Doctoral Dissertation, University of Bayreuth, Bayreuth, Germany, 1995; And Zenk, R., Doctoral Dissertation, University of Bayreuth, Bayreuth, Germany, 1994.Following paper is also described these methods: Wailes, P.C.; Coutts, R.S.P.; Weigold, H.inOrganometallic Chemistry of Titanium, Zirconium, and Hafnium, Academic; New York, 1974.; Cardin, D.J.; Lappert, M.F.; And Raston, C.L.; Chemistry of Organo-Zirconium and-Hafnium Compounds; Halstead Press; New York, 1986.The method of the metallocene compound that generation is used in can be aspect more of the present invention is open in U.S. Patent Publication No. 2007/0179044 and Application No. 12/001,733, and the open of them incorporated this paper into their full text by reference.

Activator-carrier

The present invention includes the various catalyst compositions that contain activator, activator can be activator-carrier.On the one hand, activator-carrier comprises chemically treated soild oxide.Alternatively, activator-carrier can comprise clay mineral, column clay (pillared clay), strips off type clay (exfoliated clay), be glued to the type that strips off clay, layer silicate mineral, non-layer silicate mineral, the aluminium silicate mineral of stratiform, non-layer aluminosilicate mineral or its any combination in another oxide matrix.Generally speaking, activator-carrier contains cloth Lanace platform or Lewis acid group.

Compare with the solid oxidation compounds that is untreated accordingly, chemically treated soild oxide shows the acidity of enhancing.Compare with the soild oxide that is untreated accordingly, chemically treated soild oxide also plays a part catalyst activator.Although chemically treated soild oxide activates metallocene under the shortage promotor, it is unnecessary removing promotor from catalyst composition.Compare with the catalyst composition that contains the soild oxide that is untreated accordingly, the mobilizing function of activator-carrier is tangible in the activity that strengthens catalyst composition generally.Yet, believe that chemically treated soild oxide can play the function of activator, even under the situation that does not have machine aluminium compound, aikyiaiurnirsoxan beta, organoboron compound or ionizing ionic compound etc.

Chemically treated soild oxide can comprise the soild oxide of at least a electrophilic anionic treatments of at least a usefulness.Although do not want to be subjected to the constraint of following saying, believe, the processing of soild oxide is increased or has strengthened the acidity of oxide compound with the electrophilic component.Therefore, activator-carrier shows lewis acidity or Bronsted acidity, greater than Lewis acid intensity or the Bronsted strength of acid of the soild oxide that is untreated, perhaps activator-carrier has more acid position than untreated soild oxide, or both have concurrently usually for it.A kind of method that quantizes the acidity of chemically treated and untreated solid oxide material is by comparison process and polymerization activity untreated oxide compound under acid catalyzed reaction.

Chemical treatment soild oxide of the present invention is generally formed by the inoganic solids oxide compound that shows lewis acidity or Bronsted acidity character and have a relative high porosity.Described soild oxide electrophilic component is generally the electrophilic negatively charged ion and carries out chemical treatment, to form activator-carrier.

According to an aspect of the present invention, can have pore volume more than about 0.1cc/g for the preparation of the soild oxide of chemical treatment soild oxide.According to a further aspect in the invention, described soild oxide can have the above pore volume of about 0.5cc/g.According to a further aspect of the invention, described soild oxide can have the above pore volume of about 1.0cc/g.

On the other hand, described soild oxide has about 100 to about 1000m ²The surface-area of/g.Also on the other hand, soild oxide has from about 200 to about 800m ²The surface-area of/g.Aspect another, soild oxide has from about 250 to about 600m of the present invention ²The surface-area of/g.

Chemically treated soild oxide can comprise such solid inorganic oxide, at least a element that it comprises oxygen and is selected from the 2nd, 3,4,5,6,7,8,9,10,11,12,13,14 or 15 families of the periodic table of elements perhaps comprises oxygen and at least a element that is selected from lanthanon or actinide elements.(referring to Hawley's Condensed Chemical Dictionary, 11 ^ThEd., John Wiley ﹠amp; Sons; 1995; Cotton, F.A.; Wilkinson, G.; Murillo; C.A.; And Bochmann; M.Advanced Inorganic Chemistry, 6 ^ThEd., Wiley-Interscience, 1999).For example, inorganic oxide can comprise oxygen and at least a element that is selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn or Zr.

Can be used for forming the solid oxide material of chemically treated soild oxide or the suitable example of compound includes, but not limited to Al ₂O ₃, B ₂O ₃, BeO, Bi ₂O ₃, CdO, Co ₃O ₄, Cr ₂O ₃, CuO, Fe ₂O ₃, Ga ₂O ₃, La ₂O ₃, Mn ₂O ₃, MoO ₃, NiO, P ₂O ₅, Sb ₂O ₅, SiO ₂, SnO ₂, SrO, ThO ₂, TiO ₂, V ₂O ₅, WO ₃, Y ₂O ₃, ZnO, ZrO ₂And analogue, comprise its mixed oxide, and combination.For example, described soild oxide can be silicon-dioxide, aluminum oxide, silica-alumina, aluminum phosphate, assorted poly-tungstate, titanium dioxide, zirconium white, magnesium oxide, boron oxide, zinc oxide, their mixed oxide or their any combination.

Soild oxide of the present invention comprises oxide material, for example aluminum oxide, its " oxide compound of mixing " compound such as silica-alumina and combination and its mixture.The oxide compound that mixes, silica-alumina for example can be single chemofacies or can be to have more than one to be combined with oxygen and many chemofaciess of forming the metal of solid oxidation compounds.The example that can be used in the mixed oxide in activator-carrier of the present invention includes, but are not limited to silica-alumina, silica-titania, silicon-dioxide-zirconium white, zeolite, multiple clay mineral, aluminum oxide-titanium dioxide, aluminium oxide-zirconium oxide, zinc-aluminate and analogue.

Electrophilic component for the treatment of soild oxide can be to increase the Louis of soild oxide or any component of Bronsted acidity (than the soild oxide of not using at least a electrophilic anionic treatments) after handling.According to an aspect of the present invention, described electrophilic component is the electrophilic negatively charged ion, and it derives from salt, acid or other compound, for example as the source of this negatively charged ion or the volatile organic compounds of parent.The example of electrophilic negatively charged ion includes but not limited to sulfate radical, bisulfate ion, fluorine root, chlorine root, bromine root, iodine root, fluorosulfuric acid root, fluoroboric acid root, phosphate radical, hexafluorophosphoric acid root, trifluoroacetic acid root, trifluoromethanesulfonic acid root, fluorine zirconate, hydrofluotitanic acid root and analogue, comprises their mixture and composition.In addition, other ion or the non-ionic compound as the source of these electrophilic negatively charged ion also can be used among the present invention.In one aspect of the invention, consider that the electrophilic negatively charged ion is fluorine root, chlorine root, bromine root, phosphate radical, trifluoromethanesulfonic acid root, bisulfate ion or sulfate radical etc., perhaps their any combination.

Therefore, for example, the chemically treated soild oxide that uses in the catalyst composition of the present invention can be fluorided alumina, chlorinated aluminas, bromination aluminum oxide, sulfated alumina, fluorinated silica-aluminum oxide, chlorodioxin silicon-aluminum oxide, bromination silica-alumina, sulfation silica-alumina, fluorinated silica-zirconium white, chlorodioxin silicon-zirconium white, bromination silicon-dioxide-zirconium white, sulfation silicon-dioxide-zirconium white, fluorinated silica-titanium oxide, fluorinated silica-coated aluminum oxide etc. or its combination.

When the electrophilic component comprised the salt of electrophilic negatively charged ion, the counter ion of this salt or positively charged ion can be selected from and allow this salt to reply or decompose back any positively charged ion of acid in calcination process.Control comprises as the factor of the suitability of the specific salts of electrophilic negative ion source, but be not limited to, the ion pairing effect of salt between shortage, positively charged ion and the negatively charged ion of the solvability of expectation in the solvent, positively charged ion adverse effect, give moisture-absorption characteristics and the similar characteristics of salt and the thermostability of negatively charged ion by positively charged ion.The example of suitable cation includes, but not limited to ammonium, trialkyl ammonium, tetra-allkylammonium, tetraalkyl in the salt of electrophilic negatively charged ion

H ⁺, [H (OEt ₂) ₂] ⁺And analogue.

In addition, one or more different electrophilic negatively charged ion combinations in varing proportions can be used to make the level that the concrete acidity of activator-carrier is suitable for expecting.The combination that can make the electrophilic component and oxide material contact with any order with chemical treatment soild oxide acidity that expectation is provided simultaneously or contact individually.For example, one aspect of the present invention is to use two or more electrophilic negative ion source compounds in two or more independent contact procedures.

Therefore, it is as follows to prepare the example of this quadrat method of chemically treated soild oxide: the solid oxidation compounds of selection or the combination of oxide compound are contacted, to form first mixture with the first electrophilic negative ion source compound; Calcine this first mixture, contact with the second electrophilic negative ion source compound then, to form second mixture; Calcine described second mixture afterwards, to form the solid oxidation compounds of handling.In such process, the described first and second electrophilic negative ion source compounds can be identical or different compounds.

According to a further aspect in the invention, chemically treated soild oxide comprises the combination of solid inorganic oxide material, mixed oxide material or inorganic oxide material, it is handled with the electrophilic component chemical, and randomly handle with source metal, described source metal comprises metal-salt, metal ion or other metallic compound.The non-limitative example of metal or metal ion comprises zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium etc. or their combination.Silicon-dioxide-coated aluminum oxide that the example that comprises the chemically treated soild oxide of metal or metal ion includes, but are not limited to the sulfated alumina, chlorination Zinc aluminate, the Zinc aluminate of fluoridizing, sulfation Zinc aluminate of fluorinated silica-aluminum oxide, the zinc dipping of chlorodioxin silicon-aluminum oxide, the zinc dipping of fluorided alumina, the zinc dipping of fluorided alumina, the zinc dipping of chlorinated aluminas, the titanium dipping of zinc dipping, handle with the hexafluoro metatitanic acid, with zinc processing and silicon-dioxide-coated aluminum oxide of fluoridizing then etc. or their any combination.

Any method with metal impregnation soild oxide material can be used.The method that oxide compound and source metal---normally salt or metallic compound---contact can include but not limited to that gel method, cogelled method, a kind of compound are impregnated in the another kind of compound and similar approach.If desired, metallic compound is joined or is impregnated in the soild oxide with the solution form, with being converted into loaded metal by calcining.Therefore, solid inorganic oxide may further include metal, and it is selected from the combination of zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum etc. or these metals.For example, because zinc can provide the catalyst activity of raising with low cost, zinc is often used in the dipping soild oxide.

Before soild oxide is handled with the electrophilic negatively charged ion, afterwards or simultaneously, can handle soild oxide with metal-salt or metallic compound.After any contact method, the contact mixture of oxide compound, electrophilic negatively charged ion and metal ion is calcined usually.Can be selectively, solid oxide material, electrophilic negative ion source and metal-salt or metallic compound are contacted simultaneously and are calcined.

The whole bag of tricks is used to form useful in the present invention chemically treated soild oxide.Chemically treated soild oxide can comprise the product of contact of at least a solid oxidation compounds and at least a electrophilic negative ion source.And do not require with calcining solid oxide compound before the electrophilic negative ion source contacts.Product of contact is calcined in solid oxidation compounds and electrophilic negative ion source contact process or after contacting usually.The solid oxidation compounds can be calcined or do not calcined.The whole bag of tricks that preparation can be used in the soild oxide activator-carrier among the present invention is in the news.For example, these methods are at United States Patent (USP) 6,107, and 230,6,165,929,6,294,494,6,300,271,6,316,553,6,355,594,6,376,415,6,388,017,6,391,816,6,395,666,6,524,987,6,548,441,6,548,442,6,576,583,6,613,712,6,632,894, describe in 6,667,274 and 6,750,302, its disclosure is incorporated this paper in full with it by reference.

According to an aspect of the present invention, solid oxide material carries out chemical treatment by it is contacted with at least a electrophilic component, and this electrophilic component is the electrophilic negative ion source normally.Further, solid oxide material randomly carries out chemical treatment with metal ion, and calcining then is to form the chemically treated soild oxide of containing metal or metal impregnation.According to a further aspect in the invention, solid oxide material and electrophilic negative ion source are touched and calcining simultaneously.

Oxide compound and electrophilic component, normally the method for the salt of electrophilic negatively charged ion or acid contact can include but not limited to that gel method, cogelled method, a kind of compound are impregnated into another kind of compound and similar approach thereof.Therefore, after any contact method, the contact mixture of soild oxide, electrophilic negatively charged ion and optional metal ion is calcined.

Soild oxide activator-carrier (that is chemically treated soild oxide) therefore can produce by comprising following method:

1) make the solid oxidation compounds contact to form first mixture with at least a electrophilic negative ion source compound; With

2) calcining first mixture is to form soild oxide activator-carrier.

According to another aspect of the present invention, soild oxide activator-carrier (chemically treated soild oxide) produces by comprising following method:

1) make at least a solid oxidation compounds contact to form first mixture with the first electrophilic negative ion source compound;

2) calcining first mixture is to produce first mixture of calcining;

3) make first mixture of calcining contact to form second mixture with the second electrophilic negative ion source compound; With

4) calcining second mixture is to form soild oxide activator-carrier.

According to another aspect of the invention, by being contacted with electrophilic negative ion source compound, soild oxide produces or forms chemically treated soild oxide, wherein said solid oxidation compounds before the contact electrophilic negative ion source, during or calcined afterwards, and wherein do not have aikyiaiurnirsoxan beta substantially, organic boron or organic boronic salt compound and ionizing ionic compound.

Generally under ambiance, the typical case carries out under the ambiance of drying in the calcining of the soild oxide of handling, and temperature is about 200 ℃ to about 900 ℃, carries out about 1 minute to about 100 hours time.Calcining can be carried out to about 800 ℃ temperature at about 300 ℃, or carries out to about 700 ℃ temperature at about 400 ℃ alternatively.Calcining can be carried out about 1 hour to about 50 hours, or about 3 hours to about 20 hours.Therefore, for example, calcining can be carried out about 1 to about 10 hours to about 550 ℃ temperature at about 350 ℃.During calcining, can use any suitable ambiance.Generally speaking, calcining is carried out under oxidizing atmosphere, for example air.Alternatively, can use inert atmosphere, for example nitrogen or argon, perhaps reducing atmosphere, for example hydrogen or carbon monoxide.

According to an aspect of the present invention, solid oxide material is handled with the source of the combination of halogen ion, sulfate ion or negatively charged ion, and chooses wantonly and handle with metal ion, calcines to provide the chemically treated soild oxide of particulate solid form then.For example, the soild oxide material can be handled with the source (being called " sulfating agent (sulfating agent) ") of vitriol, the source (being called " chlorizating agent (chloriding agent) ") of chlorion, source (being called " fluorizating agent (fluoriding agent) ") or their combination of fluorion, and calcining is to provide the soild oxide activator.Useful acidic activator-carrier includes but not limited to: the bromination aluminum oxide; Chlorinated aluminas; Fluorided alumina; Sulfated alumina; The bromination silica-alumina; Chlorodioxin silicon-aluminum oxide; Fluorinated silica-aluminum oxide; The sulfation silica-alumina; Bromination silicon-dioxide-zirconium white; Chlorodioxin silicon-zirconium white; Fluorinated silica-zirconium white; Sulfation silicon-dioxide-zirconium white; Fluorinated silica-titanium dioxide; Aluminum oxide with the processing of hexafluoro metatitanic acid; Silicon-dioxide-coated aluminum oxide with the processing of hexafluoro metatitanic acid; Silica-alumina with the hexafluoro zirconate processing; Fluorinated boron-aluminum oxide; Silicon-dioxide with the processing of hexafluoro boric acid; Aluminum oxide with the Tetrafluoroboric acid processing; Aluminum oxide with the phosphofluoric acid processing; Column clay, for example the column montmorillonite is optional with fluorochemical, muriate or vitriol processing; Phosphorylation aluminum oxide or other aluminate or phosphate (almninophosphate), optional with vitriol, fluorochemical or chloride treatment; Perhaps above-mentioned any combination.In addition, any these activator-carriers can be chosen wantonly with metal ion and handle.

Chemically treated soild oxide can comprise the fluorinated solid oxide compound of particulate solid form.By soild oxide is contacted with fluorizating agent, can form the fluorinated solid oxide compound.By in suitable solvent, forming the slurries of oxide compound, fluoride ion can be added in the oxide compound, described solvent is alcohol or water for example, includes but not limited to the alcohol of 1 to 3 carbon, because they have volatility and low surface tension.The example of suitable fluorizating agent includes, but are not limited to hydrofluoric acid (HF), Neutral ammonium fluoride (NH ₄F), ammonium bifluoride (NH ₄HF ₂), tetrafluoro boron ammonium (ammonium tetrafluoroborate) (NH ₄BF ₄), ammonium silicofluoride (ammonium silicofluoride (hexafluorosilicate (hexafluorosilicate)) ((NH ₄) ₂SiF ₆), ammonium hexafluorophosphate (NH ₄PF ₆), hexafluoro metatitanic acid (H ₂TiF ₆), ammonium hexa-fluorotitanate ((NH ₄) ₂TiF ₆), hexafluoro zirconate (H ₂ZrF ₆), its analogue and combination thereof.For example, ammonium bifluoride NH ₄HF ₂Can be used as fluorizating agent, reason is that it is easy to use and can obtains.

If expectation, soild oxide is handled with fluorizating agent during calcining step.Can use any fluorizating agent that during calcining step, can fully contact soild oxide.For example, except foregoing those fluorizating agents, can use the organic fluorizating agent of volatility.The example of the useful organic fluorizating agent of volatility includes but not limited to freonll-11, perflexane (perfluorohexane), perfluor benzene (perfluorobenzene), methyl fuoride, trifluoroethanol etc. and their combination in this aspect of the present invention.If in calcining, fluoridize, also can use gaseous hydrogen fluoride or fluorine itself with soild oxide.A kind of method easily that soild oxide is contacted with fluorizating agent is to make fluorizating agent be evaporated to air-flow for the fluidized solids oxidation thing during calcining.

Equally, in another aspect of this invention in, chemically treated soild oxide comprises the chlorination soild oxide that is in solid particulate form.By soild oxide is contacted with chlorizating agent, form the chlorination soild oxide.By in suitable solvent, forming the slurries of oxide compound, chloride ion can be added in the oxide compound.Soild oxide can be handled with chlorizating agent during calcining step.During calcining step can as muriate source and fully any chlorizating agent of catalytic oxidation thing can be used.For example, can use the agent of volatility organic chloride.The example of suitable volatility organic chloride agent includes but not limited to some freonll-11, perna (perchlorobenzene), methyl chloride, methylene dichloride, chloroform, tetracol phenixin, ethapon etc. or their any composition.During calcining, itself also can use gaseous hydrogen chloride or chlorine with soild oxide.A kind of method easily that oxide compound is contacted with chlorizating agent is to make chlorizating agent be evaporated to air-flow for the fluidized solids oxidation thing during calcining.

The fluorochemical that existed before the calcining solid oxide compound or the amount of chloride ion are generally by weight from about 2% to about 50%, and wherein this weight percent is based on soild oxide before the calcining such as the weight of silica-alumina.According to a further aspect in the invention, the fluorochemical that existed before the calcining solid oxide compound or the amount of chloride ion are calculated by weight to about 3% to about 25%, and according to a further aspect in the invention, are calculated by weight to about 4% to about 20%.In case flood with halogenide, the halogenation oxide compound can be come dry by any suitable method, the filtration (suction filtration) that includes but not limited to bleed evaporates afterwards, dry under vacuum, spraying drying and similar approach, although the soild oxide of moist dipping and to begin calcining step at once also be possible.

Generally have greater than the about pore volume of 0.5cc/g for the preparation of the silica-alumina of the silica-alumina of handling.According to an aspect of of the present present invention, pore volume is greater than about 0.8cc/g with according to another aspect of the present invention, greater than about 1.0cc/g.Further, silica-alumina generally has greater than about 100m ²The surface-area of/g.According to another aspect of the present invention, surface-area is greater than about 250m ²/ g.More on the other hand, surface-area is greater than about 350m ²/ g.

The silica-alumina that uses among the present invention generally has calculates by weight from about 5% to about 95% alumina content.According to an aspect of of the present present invention, the alumina content of silica-alumina is calculated by weight from about 5% to about 50% aluminum oxide or calculate by weight from about 8% to about 30% aluminum oxide.On the other hand, can use the silica-alumina compound of high alumina content, wherein the alumina content of these silica-alumina compounds calculate by weight general range for from about 60% to about 90% aluminum oxide or calculate by weight from about 65% to about 80% aluminum oxide.According on the other hand of the present invention, the soild oxide composition comprises the aluminum oxide that do not have silicon-dioxide and according to another aspect of the present invention, the soild oxide composition comprises the silicon-dioxide that does not have aluminum oxide.

Sulfated soild oxide comprises vitriol and soild oxide component for example aluminum oxide or silica-alumina, is the form of granular solids.Randomly, the sulfation oxide compound is further handled with metal ion, so that the sulfation oxide compound of calcining contains metal.According to an aspect of the present invention, the sulfation soild oxide comprises vitriol and aluminum oxide.In some cases, sulfated alumina be by aluminum oxide wherein with sulfate source for example the method handled of sulfuric acid or vitriol such as ammonium sulfate form.General carry out this process by forming aluminum oxide at suitable solvent slurries in alcohol or the water for example, in described solvent, the sulfating agent of expectation concentration is added into.Appropriate organic solvent includes, but are not limited to the alcohol of 1 to 3 carbon, and reason is their volatility and low surface tension.

According to an aspect of the present invention, the amount of the sulfate ion that exists before calcining is for about 100 parts by weight soild oxide, for by weight about 0.5 part to about 100 parts sulfate ion.According to a further aspect in the invention, the amount of the sulfate ion that exists before calcining is for about 100 parts by weight soild oxide, for by weight about 1 part to about 50 parts sulfate ion, and according to of the present invention still on the other hand, for about 100 parts by weight soild oxide, for by weight about 5 parts to about 30 parts sulfate ion.These weight ratio are based on the weight of the soild oxide before the calcining.In case with vitriol dipping, the sulfation oxide compound can be come dry by any suitable method, include but not limited to bleed filter after evaporation, dry under vacuum, spraying drying and similar approach, also be possible although get started calcining step.

According to another aspect of the present invention, but prepare activator-carrier that the activator-carrier that uses in the catalyst composition of the present invention comprises ion-exchange, include but not limited to silicon-dioxide stratiform or non-laminate structure and aluminosilicate compound or mineral and its combination.In other one side of the present invention, but aluminosilicate ion-exchange, stratiform such as column clay are used as activator-carrier.When but acidic activator-carrier comprised the activator of ion-exchange-carrier, it optionally disclosed those electrophilic anionic treatments with at least a for example this paper, though but the activator-carrier of ion-exchange generally without the electrophilic anionic treatments.

According to another aspect of the present invention, activator-carrier of the present invention comprises the clay mineral of the layer that has exchangeable cation and can expand.But general clay mineral activator-carrier includes but not limited to aluminosilicate ion-exchange, stratiform, for example column clay.Though use term " carrier ", it is not intended to be interpreted as the inert fraction in the catalyst composition, and it is considered the active part of catalyst composition on the contrary, because itself and metallocene composition are closely united.

According to another aspect of the present invention, clay material of the present invention comprises the material of their state of nature or the material of having handled by wetting, ion-exchange or postization (pillaring) with various ions.Typically, clay material activator-carrier of the present invention comprises the clay of using big cationic exchange, comprises multinuclear, high electric charge metal complex positively charged ion.Yet, clay material activator-carrier of the present invention also comprises the clay of having used simple salt ion-exchange, simple salt includes but not limited to the salt of Al (III), Fe (II), Fe (III) and Zn (II) and part, as halogenide, acetate, vitriol, nitrate or nitrite.

According to a further aspect in the invention, activator-carrier comprises column clay.Term " column clay " is used in reference to the clay material that carries out ion-exchange with high electric charge metal complexes positively charged ion big, that the typical case is multinuclear.The example of such ion includes, but are not limited to have for example Keggin ion, various polyoxometallate and other heavy ion of 7+ electric charge.Therefore, term postization (pillaring) refers to simple permutoid reaction, and wherein the exchangeable cation of clay material is by big high charge ion such as Keggin ion exchange.Then, these polymerizing cationicallies are fixed in the interlayer of clay, and are converted into metal oxide " post " when calcining, are effective as columnar structure (column-like structures) and support clay seam.Therefore, clay is dried and calcines and after producing pillar stiffener between the clay seam, the lattice structure of expansion is kept, and porosity is improved.Formed hole can be used as the function of post material and employed female clay material and changes in shape and size.The example of postization and column clay finds in following document: T.J.Pinnavaia, Science220 (4595), 365-371 (1983); J.M.Thomas, Intercalation Chemistry, (S.Whittington and A.Jacobson edit) Ch.3, pp.55-99, Academic Press, Inc., (1972); United States Patent (USP) the 4th, 452, No. 910; United States Patent (USP) the 5th, 376, No. 611; With United States Patent (USP) the 4th, 060, No. 480; Its disclosure is incorporated this paper in full with it by reference.

The utilization of post method has the clay mineral of exchangeable cation and the layer that can expand.Can use any column clay that in catalyst composition of the present invention, can strengthen olefinic polymerization.Therefore, the suitable clay mineral for postization includes, but are not limited to: diaspore English; Terre verte, dioctahedron (Al) and trioctahedron (Mg) and derivative thereof if you would take off stone (wilkinite), nontronite, hectorite or lithium magnesium silicate (laponites); Halloysite; Vermiculite; Mica; Fluoronated mica (fluoromicas); Chlorite; Mixed layer clay; Fibrous clay includes but not limited to sepiolite, attapulgite and polygorskite (palygorskites); Serpentine clay (serpentine clay); Illite; Lithium magnesium silicate; Talcum powder; With their any composition.In one aspect, column clay activator-carrier comprises wilkinite or montmorillonite.Bentonitic main component is montmorillonite.

If desired, column clay can be pretreated.For example, before adding polymerization reactor, pillared bentonite by at inert atmosphere, be typically under the drying nitrogen and carried out pre-treatment down in dry about 3 hours in 300 ℃.Although described exemplary pre-treatment at this, should be appreciated that pre-treatment can carry out under many other temperature and times, comprise any combination of temperature and time step, all these comprises in the present invention.

Promoting agent-carrier for the preparation of catalyst composition of the present invention can be combined with other inorganic carrier material, includes but not limited to zeolite, inorganic oxide, phosphorylation inorganic oxide etc.On the one hand, the typical carriers material of use includes but not limited to earth silicon/titanic oxide, its mixture or its arbitrary combination of silicon-dioxide, silica-alumina, aluminum oxide, titanium dioxide, zirconium white, magnesium oxide, boron oxide (boria), Thorotrast, aluminophosphates, aluminum phosphate, silica-titania, co-precipitation.

According to a further aspect in the invention, one or more of metallocene compounds can contact for first period with organo-aluminium compound in advance with olefinic monomer, and this mixture is contacted with activator-carrier.In case the preceding contact mixture of metallocene compound (one or more), olefinic monomer and organo-aluminium compound is with after activator-carrier contacts, the composition that further comprises activator-carrier is called as " back contact " mixture.Be added into before carrying out the reactor of polymerization process therein, can making this back contact mixture keep further second period of contact.

According on the other hand of the present invention, one or more metallocene compounds can with olefinic monomer and activator-carrier before contacted for first period, this mixture is contacted with organo-aluminium compound.In case the preceding contact mixture of metallocene compound (one or more), olefinic monomer and activator-carrier contacts with organo-aluminium compound, " back contact " mixture that comprises also that the composition of organoaluminum is called.Back contact mixture can be allowed to keep contacting further second period before being introduced into polymerization reactor.

Organo-aluminium compound

On the one hand, catalyst composition of the present invention can include machine aluminium compound.These compounds include but not limited to have the compound of following formula:

(R ⁶) ³Al；

R wherein ⁶It is the aliphatic group with from 2 to 10 carbon atoms.For example, R ⁶Can be ethyl, propyl group, butyl, hexyl or isobutyl-.

Other organo-aluminium compound that can use in catalyst composition disclosed herein can include but not limited to have the compound of following formula:

Al(X ⁵) _m(X ⁶) _3-m，

X wherein ⁵It is alkyl; X ⁶Be alkoxyl group or aryloxy, halogen or hydride ion; With m be from 1 to 3, comprise 1 and 3.

On the one hand, X ⁵Be to have from 1 alkyl to about 20 carbon atoms.At other one side of the present invention, X ⁵It is the alkyl with from 1 to 10 carbon atom.For example, on the other hand of the present invention, X ⁵Can be ethyl, propyl group, normal-butyl, the tertiary butyl, isobutyl-or hexyl etc.

According to an aspect of of the present present invention, X ⁶Be alkoxyl group or aryloxy---its any have from 1 to 20 carbon atom, halogen or hydride ion.In another aspect of this invention, X ⁶Be independently selected from fluorine or chlorine.More on the other hand, X ⁶Be chlorine.

Formula Al (X ⁵) _m(X ⁶) _3-mIn, m is from 1 to 3 number, comprises 1 and 3, typically m is 3.The value of m is not limited to integer; Therefore, this formula comprises sesquihalide compound or other organoaluminum duster compound.

The example that is fit to the organo-aluminium compound that uses according to the present invention includes but not limited to trialkyl aluminium compound, dialkyl monohalide aluminum compound (dialkylaluminium halide compounds), aluminum dialkyl alkanol compound (dialkylaluminum alkoxide compounds), hydrogenation aluminum dialkyl compound (dialkylaluminum hydride compounds) and their composition.The concrete indefiniteness example of suitable organo-aluminium compound includes but not limited to: trimethyl aluminium (TMA), triethyl aluminum (TEA), tri-n-n-propyl aluminum (TNPA), three n-butylaluminum (TNBA), triisobutyl aluminium (TIBA), tri-n-hexyl aluminum, tri-n-octylaluminium, diisobutylaluminium hydride, diethyl aluminum ethylate (diethylaluminum ethoxide), diethylaluminum chloride etc. or its combination.

The present invention consider to make contact before at least a bridged combined metal compound and at least a organo-aluminium compound and the olefinic monomer form before contact mixture, be somebody's turn to do preceding contact mixture contact the formation catalyst composition with activator-carrier method then.When catalyst composition prepares by this way, typically but not necessarily, before a part of organo-aluminium compound is added in the contact mixture and other a part of organo-aluminium compound be added in the back contact mixture for preparing when current contact mixture contacts with soild oxide activator-carrier.Yet all organo-aluminium compound can be used for preparing catalyst composition in the step of preceding contact or back contact.Alternatively, all catalyst components contact in single step.

Further, in preceding contact or back contact procedure, can use more than a kind of organo-aluminium compound.When organo-aluminium compound in a plurality of steps, add fashionable, the organo-aluminium compound that used in the contact mixture contact and back before the amount of organo-aluminium compound disclosed herein was included in and the total amount that is added to any other organo-aluminium compound in the polymerization reactor.Therefore, disclosed is the total amount of organo-aluminium compound, and no matter use single organo-aluminium compound or more than one organo-aluminium compound.

Aluminium alkoxide compound

The present invention uses the catalyst composition that contains activator, and the invention some aspect, activator comprises at least a aluminium alkoxide compound, at least a organic boron or organic boronic salt compound or at least a ionizing ionic compound or its arbitrary combination.As used herein, term " aikyiaiurnirsoxan beta " refers to the kind of aluminium alkoxide compound, composition, mixture or separation, and does not consider how this class aikyiaiurnirsoxan beta is prepared, forms or provide in addition.For example, the catalyst composition that contains aluminium alkoxide compound can be produced, wherein aikyiaiurnirsoxan beta is provided as gathering (alkyl aluminum oxide) (poly (hydrocarbyl aluminum oxides)), and perhaps wherein aikyiaiurnirsoxan beta is provided as alkylaluminium cpd and for example combination of water of active proton source.Aikyiaiurnirsoxan beta is also referred to as poly-(alkyl aluminum oxide) or Organoaluminoxy alkane (organoaluminoxanes).

Usually, other catalyst component is contacted in saturated hydrocarbon compound solvent with aikyiaiurnirsoxan beta, although can use any solvent to the basic inertia of product of reactant, intermediate and activation step.Formed catalyst composition can be collected by any suitable method in this way, includes but not limited to filter.Alternatively, catalyst composition is introduced in the polymerization reactor without separation.

Aluminium alkoxide compound of the present invention can be oligomeric aluminum compound, and it comprises linear structure, ring texture or cage structure, perhaps the mixture of all these three kinds of structures.Ring-type aluminium alkoxide compound with following formula be the present invention includes:

Wherein R is straight chain or the branched-alkyl with 1 to 10 carbon atom, and p is 3 to about 20 integer.The AlRO part that is presented at this has also been formed the repeating unit in the line style aikyiaiurnirsoxan beta.Therefore, the line style aikyiaiurnirsoxan beta with following formula also be the present invention includes:

Wherein R is that to have the linearity of from 1 to 10 carbon atom or branched-chain alkyl and q be from 1 to 50 integer.

Further, aikyiaiurnirsoxan beta can have formula R ^t _{5r+ α}R ^b _R-αAl _4rO _3rCage structure, R wherein ^tBe terminal linearity or the branched alkyl group with 1 to 10 carbon atom; R ^bBe bridging linearity or the branched alkyl group with 1 to 10 carbon atom; R is 3 or 4; Equal n with α _{Al (3)}-n _{O (2)}+ n _{O (4)}, n wherein _{Al (3)}Be the number of three-fold coordination aluminium atom, n _{O (2)}Be the number of two coordination Sauerstoffatoms, and n _{O (4)}It is the number of 4 coordination Sauerstoffatoms.

Therefore, the aikyiaiurnirsoxan beta that can use in catalyst composition of the present invention generally uses formula as (R-Al-O) _p, R (R-Al-O) _qAlR ₂Deng expression.In these formulas, the R group is generally straight chain or branching C _l-C ₆Alkyl, for example methyl, ethyl, propyl group, butyl, amyl group or hexyl.The example of applicable aluminium alkoxide compound includes but not limited to methylaluminoxane, ethyl aikyiaiurnirsoxan beta, n-propyl aikyiaiurnirsoxan beta, sec.-propyl aikyiaiurnirsoxan beta, normal-butyl alumina alkane, tertiary butyl aikyiaiurnirsoxan beta, sec-butyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, 1-amyl group aikyiaiurnirsoxan beta, 2-amyl group aikyiaiurnirsoxan beta, 3-amyl group aikyiaiurnirsoxan beta, isopentyl aikyiaiurnirsoxan beta, neo-pentyl aikyiaiurnirsoxan beta etc. or their any combination according to the present invention.Methylaluminoxane (MAO), ethyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide are to prepare from trimethyl aluminium, triethyl aluminum or triisobutyl aluminium respectively, and are called as poly-(methyl oxidation aluminium) (poly (methyl aluminum oxide)), poly-(ethyl aluminum oxide) (poly (ethyl aluminum oxide) and poly-(isobutyl-aluminum oxide) (poly (isobutyl aluminum oxide)) sometimes respectively.Use aikyiaiurnirsoxan beta also within the scope of the invention with trialkylaluminium, for example be disclosed in U.S. Patent number 4,794, in 096, it all is incorporated herein with it by reference.

The present invention considers respectively at aikyiaiurnirsoxan beta formula (R-Al-O) _pAnd R (R-Al-O) _qAlR ₂In p and a plurality of values of q.Some aspects, p and q are 3 at least.Yet, depend on how to prepare, store and use aikyiaiurnirsoxan beta, in the monocyte sample of aikyiaiurnirsoxan beta, the value of p and q can change, and this paper considers these combinations of Organoaluminoxy alkane.

Contain in the catalyst composition of aikyiaiurnirsoxan beta in preparation, the mol ratio of the total mole number of the total mole number of the aluminium in the aikyiaiurnirsoxan beta in the composition (or multiple aikyiaiurnirsoxan beta) and metallocene compound (or multiple metallocene compound) is generally at about 1:10 and about 100, between the 000:1.On the other hand, mol ratio be from about 5:1 to about 15, the scope of 000:1.Randomly, aikyiaiurnirsoxan beta can with from about 0.01mg/L to about 1000mg/L, from about 0.1mg/L to about 100mg/L or the scope from about 1mg/L to about 50mg/L be added to polymeric area.

Can prepare Organoaluminoxy alkane by the whole bag of tricks.The example of Organoaluminoxy alkane preparation is disclosed in U.S. Patent number 3,242, and in 099 and 4,808,561, its disclosure is all introduced by reference at this.For example, the water in inert organic solvents can with alkylaluminium cpd (R for example ⁶) ₃Al reacts and the Organoaluminoxy hydride compounds of formation expectation.Although do not expect to be bound by this statement, it is believed that this kind synthetic method can provide the mixture of line style and ring-type R-Al-O aikyiaiurnirsoxan beta kind, these two kinds of aikyiaiurnirsoxan beta all be the present invention includes.Alternatively, by making for example (R of alkylaluminium cpd ⁶) ₃Al and salt hydrate for example hydrated copper sulfate react in inert organic solvents, can prepare Organoaluminoxy alkane.

Organic boron/organic boronic salt compound

According to another aspect of the present invention, catalyst composition can comprise organic boron or organic boronic salt activator.Organic boron or organic boronic salt compound comprise neutral boron compound, borate etc. or its combination.For example, consider to fluoridize organoboron compound and fluoridize the organic boronic salt compound.

The present invention can use the organic boron of any fluorine or fluorine organic boronic salt compound.The example that can be used to the fluorine organic boronic salt compound among the present invention includes but not limited to fluoro aryl borate (fluorinated aryl borates), N for example, accelerine four (pentafluorophenyl group) borate (N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate), triphenylcarbenium Four (pentafluorophenyl group) borate (triphenylcarbenium tetrakis (pentafluorophenyl) borate), four (pentafluorophenyl group) lithium tetraborate (lithium tetrakis (pentafluorophenyl) borate), N, accelerine four [3, two (trifluoromethyl) phenyl of 5-] borate (N, N-dimethylanilinium tetrakis[3,5-bis (trifluoromethyl) phenyl] borate), triphenylcarbenium Four [two (trifluoromethyl) phenyl of 3,5-] borate (triphenylcarbeniumtetrakis[3,5-bis (trifluoromethyl) phenyl] borate) and analogue, or their mixture.The example that can be used to fluorine organoboron compound of the present invention includes but not limited to three (pentafluorophenyl group) boron (tris (pentafluorophenyl) boron), three [3, two (trifluoromethyl) phenyl of 5-] boron (tris[3,5-bis (trifluoromethyl) phenyl] boron) and analogue, or their mixture.Although do not expect to be bound by following theory, these examples of fluorine organic borate and fluorine organoboron compound and related compound are considered to when formed " weak coordination (weakly-coordinating) " negatively charged ion when organo-metallic or metallocene compound are combined, as at U.S. Patent number 5,919, open in 983, it is all introduced by reference at this.The applicant also considers to use the difunctional compound that contains two or more boron atoms in two boron or two boron compound or other chemical structure, as at J.Am.Chem.Soc., 2005,127, disclosed among the pp.14756-14768, its content is incorporated this paper by reference in full into.

Generally speaking, can use the organoboron compound of any amount.According to an aspect of of the present present invention, the mol ratio of the total mole number of the total mole number of organic boron or organic boronic salt compound (or multiple compound) and metallocene compound (or multiple metallocene compound) is the scope from about 0.1:1 to about 15:1 in the catalyst composition.Typically, the amount of fluoridizing organic boron or fluoridizing the organic boronic salt compound of use be every mole of metallocene compound about 0.5 mole to about 10 moles boron/borate compound.According to another aspect of the present invention, the amount of fluoridizing organic boron or fluoridizing the organic boronic salt compound be every mole of metallocene compound about 0.8 mole to about 5 moles boron/borate compound.

The ionizing ionic compound

The present invention further provides the catalyst composition that can comprise the ionizing ionic compound.The ionizing ionic compound is to play the activator of enhancing catalyst composition activity or the ionic compound of promotor function.Although be not bound by theory, it is believed that, described ionizing ionic compound can be converted into one or more cationic metallocene compounds with the metallocene compound reaction and with metallocene, or early stage cationic metallocene compound (incipient cationic metallocene compounds).Equally, although do not expect to be bound by theory, it is believed that this ionizing ionic compound can play a part the ionizing compound by completely or partially extracting anion ligand from metallocene, described anion ligand may be non-alkadienyl part, for example X.Yet the ionizing ionic compound is activator, and no matter its ionization metallocene is captured the X part in the mode that forms ion pair, weakens the metal-X key in the metallocene, simply with the coordination of X part, still by some other mechanism activation metallocene compound.

In addition, the ionizing ionic compound needn't only activate metallocene compound.Compare with the catalyst composition that does not comprise the ionizing ionic compound, the mobilizing function of ionizing ionic compound can be tangible on the activity that strengthens catalyst composition generally.

The example of ionizing ionic compound includes but not limited to following compound: three (normal-butyl) ammonium four (p-methylphenyl) borate, three (normal-butyl) ammonium four (tolyl) borate, three (normal-butyl) ammonium four (2, the 4-3,5-dimethylphenyl) borate, three (normal-butyl) ammonium four (3, the 5-3,5-dimethylphenyl) borate, three (normal-butyl) ammonium four [3, two (trifluoromethyl) phenyl of 5-] borate, three (normal-butyl) ammonium four (pentafluorophenyl group) borate, N, N-dimethyl puratized agricultural spray four (p-methylphenyl) borate, N, N-dimethyl puratized agricultural spray four (tolyl) borate, N, N-dimethyl puratized agricultural spray four (2, the 4-3,5-dimethylphenyl) borate, N, N-dimethyl puratized agricultural spray four (3, the 5-3,5-dimethylphenyl) borate, N, N-dimethyl puratized agricultural spray four [3, two (trifluoromethyl) phenyl of 5-] borate, N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borate, triphenylcarbenium Four (p-methylphenyl) borate, triphenylcarbenium

Four (tolyl) borate, triphenylcarbenium Four (2,4-3,5-dimethylphenyl) borate, triphenylcarbenium

Four (3,5-3,5-dimethylphenyl) borate, triphenylcarbenium

Four [two (trifluoromethyl) phenyl of 3,5-] borate, triphenylcarbenium

Four (pentafluorophenyl group) borate,

Four (p-methylphenyl) borate,

Four (tolyl) borate,

Four (2,4-3,5-dimethylphenyl) borate,

Four (3,5-3,5-dimethylphenyl) borate, Four [two (trifluoromethyl) phenyl of 3,5-] borate, Four (pentafluorophenyl group) borate, four (pentafluorophenyl group) lithium tetraborate, four (phenyl) lithium tetraborate, four (p-methylphenyl) lithium tetraborate, four (tolyl) lithium tetraborate, four (2, the 4-3,5-dimethylphenyl) lithium tetraborate, four (3, the 5-3,5-dimethylphenyl) lithium tetraborate, LiBF4, four (pentafluorophenyl group) Sodium Tetraborate, sodium tetraphenylborate, four (p-methylphenyl) Sodium Tetraborate, four (tolyl) Sodium Tetraborate, four (2, the 4-3,5-dimethylphenyl) Sodium Tetraborate, four (3, the 5-3,5-dimethylphenyl) Sodium Tetraborate, sodium tetrafluoroborate, four (pentafluorophenyl group) potassium borate, potassium tetraphenylboron, four (p-methylphenyl) potassium borate, four (tolyl) potassium borate, four (2, the 4-3,5-dimethylphenyl) potassium borate, four (3, the 5-3,5-dimethylphenyl) potassium borate, potassium tetrafluoroborate, four (pentafluorophenyl group) lithium aluminate, the tetraphenyl lithium aluminate, four (p-methylphenyl) lithium aluminate, four (tolyl) lithium aluminate, four (2, the 4-3,5-dimethylphenyl) lithium aluminate, four (3, the 5-3,5-dimethylphenyl) lithium aluminate, the tetrafluoro lithium aluminate, four (pentafluorophenyl group) sodium aluminate, the tetraphenyl sodium aluminate, four (p-methylphenyl) sodium aluminate, four (tolyl) sodium aluminate, four (2, the 4-3,5-dimethylphenyl) sodium aluminate, four (3, the 5-3,5-dimethylphenyl) sodium aluminate, the tetrafluoro sodium aluminate, four (pentafluorophenyl group) potassium aluminate, the tetraphenyl potassium aluminate, four (p-methylphenyl) potassium aluminate, four (tolyl) potassium aluminate, four (2, the 4-3,5-dimethylphenyl) potassium aluminate, four (3,5-3,5-dimethylphenyl) potassium aluminate, ptfe aluminum potassium and analogue or their combination.Useful in the present invention ionizing ionic compound is not limited to these; Other example of ionizing ionic compound is disclosed in U.S. Patent number 5,576, and in 259 and 5,807,938, their disclosure is all introduced by reference at this.

Olefinic monomer

Can typically comprise that each molecule has about 2 to 30 carbon atoms and the olefin(e) compound with at least one olefinic double bonds with the unsaturated reactant that catalyst composition of the present invention and polymerization process use.The present invention includes and use olefinic monomer for example ethene or propylene and the binary copolymerization reaction of at least a different olefin(e) compound and higher reaction (for example, terpolymer is reacted).For example, the ethene copolymer of formation, terpolymer etc. generally comprise 50 moles of % of relatively large ethene (〉) and comonomer (＜50 moles of %) in a small amount, though this and do not require.Can in their molecular chains, have 3 to 20 carbon atoms with the comonomer of ethene binary copolymerization usually.

Acyclic, ring-type, many rings, terminal (α), centre, straight chain, branching, replacement, unsubstituted, functionalized can being used among the present invention with non-functionalized alkene.For example, can include but not limited to ethene with the typical unsaturated compound of catalyst composition polymerization of the present invention, propylene, 1-butylene, 2-butylene, 3-methyl-1-butene, iso-butylene, the 1-amylene, the 2-amylene, the 3-Methyl-1-pentene, 4-methyl-1-pentene, the 1-hexene, the 2-hexene, the 3-hexene, 3-ethyl-1-hexene, the 1-heptene, the 2-heptene, the 3-heptene, four kinds of positive octenes (the four normal octenes), four kinds of positive nonenes (the four normal nonenes), any two or more mixture of five kinds of positive decene (the five normal decenes) and analogue or these compounds.Ring-type and bicyclic alkene include but not limited to that cyclopentenes, tetrahydrobenzene, norbornylene, norbornadiene and analogue also can be aggregated, as mentioned above.Also can use vinylbenzene as monomer among the present invention.

When expectation copolymer (or alternatively, terpolymer), olefinic monomer can comprise ethene or the propylene that for example carries out binary copolymerization with at least a comonomer.According to an aspect of of the present present invention, the olefinic monomer in the polymerization process is ethene.In this respect, the example of suitable olefin comonomer includes but not limited to propylene, 1-butylene, 2-butylene, 3-methyl-1-butene, iso-butylene, 1-amylene, 2-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, vinylbenzene etc. or its combination.According to an aspect of of the present present invention, described at least a comonomer is selected from 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene or vinylbenzene or its arbitrary combination.

Generally speaking, introducing in the reaction zone with the amount of the comonomer that produces multipolymer is about 0.01 comonomer to about 50 weight % based on the gross weight of monomer and comonomer.According to another aspect of the present invention, based on the gross weight of monomer and comonomer, the amount that is incorporated into the comonomer in the reactor zone is about 0.01 comonomer to about 40 weight %.Still on the other hand, based on the gross weight of monomer and comonomer, the amount that is incorporated into the comonomer in the reactor zone is about 0.1 comonomer to about 35 weight %.More on the other hand, based on the gross weight of monomer and comonomer, the amount that is incorporated into the comonomer of reactor zone is about 0.5 to about 20 weight % comonomer.

Although do not expect to be bound by this theory, branching, replacement or functional olefines be used as under the situation of reactant, it is believed that the steric hindrance polymerization process that can stop and/or slow down.Therefore, the branching of desired distance carbon-carbon double bond alkene to a certain degree and/or circular part (one or more) will be not can not hinder reaction to be in more the mode that identical alkene substituting group near carbon-carbon double bond may hinder this reaction.In addition, catalyst composition of the present invention and method can be used in the polymerization of diolefinic compound, and described diolefinic compound includes but not limited to 1,3-butadiene, isoprene, 1,4-pentadiene and 1,5-hexadiene.

Catalyst composition

The present invention uses the catalyst composition that comprises the bridged combined metal compound.A kind of such catalyst composition comprises the product of contact of at least a metallocene compound and at least a activator.This catalyst composition can also comprise at least a organo-aluminium compound.Suitable activator can include but not limited to activator-carrier, aluminium alkoxide compound, organic boron or organic boronic salt compound, ionizing ionic compound etc. or its combination.

These catalyst compositions can be used for the application of various end-uses for generation of polyolefine such as ethylene copolymer.At least a metallocene compound in these catalyst compositions has following formula:

Wherein:

M ¹Be Ti, Zr or Hf;

E is C or Si;

R ⁴It is the alkyl or alkenyl group with 10 carbon atoms of as many as; With

According to these and other aspect of the present invention, consider that catalyst composition disclosed herein can contain other bridging or bridged combined metal compound and more than a kind of activator not.In addition, also consider more than a kind of organo-aluminium compound.

Catalyst composition among the present invention on the other hand comprises at least a product of contact with the metallocene compound of formula (I), at least a activator-carrier and at least a organo-aluminium compound, and wherein this catalyst composition does not have aikyiaiurnirsoxan beta, organic boron or organic boronic salt compound and ionizing ionic compound substantially.In this respect, catalyst composition is at the catalyst activity that does not have to have under these other materials following discussion.

Yet in other side of the present invention, these compounds can be used as activator.For example, consider to comprise the catalyst composition of at least a metallocene compound and at least a activator, and in this respect, activator is aluminium alkoxide compound, organic boron or organic boronic salt compound, ionizing ionic compound or its arbitrary combination.Can exist more than a kind of activator or promotor in the catalyst composition.

Catalyst composition among the present invention more on the other hand comprises a kind of the have metallocene compound of formula (I) and the product of contact of at least a activator.Just, at this respect of the present invention, catalyst composition only comprises a kind of metallocene compound, and described a kind of metallocene compound has formula (I).Randomly, this catalyst composition can also comprise at least a organo-aluminium compound.For example, the useful catalysts composition can (for example have the metallocene compound of formula (I), a kind of activator-carrier by a kind of substantially among the present invention, chemically treated soild oxide) and a kind of organo-aluminium compound (for example, TIBA) form, wherein do not have other material in the catalyst composition, this never exists the catalyst activity of the catalyst composition of described material can increase/reduce activity more than about 10% catalyst composition.

The present invention also comprises the method for preparing catalyst composition disclosed herein, for example, and as contacting each catalyst component with random order or order.

In one aspect of the invention, if necessary, at least a metallocene compound can---not necessarily be wanted olefinic monomer or the comonomer of copolymerization---and contact for first period before the organo-aluminium compound with olefinic monomer, and this preceding contact mixture is contacted with activator-carrier.First period that contacts between metallocene compound or multiple metallocene compound, olefinic monomer and the organo-aluminium compound---preceding duration of contact---typically from about 0.05 hour to about 24 hours period, for example, from about 0.05 hour to about 1 hour.Also can use from about 10 minutes to about 30 minutes preceding duration of contact.

In other one side of the present invention, at least a metallocene compound can with olefinic monomer and activator-carrier before contacted for first period, this preceding contact mixture is contacted with organo-aluminium compound.First period that contacts between metallocene compound or multiple metallocene compound, olefinic monomer and the activator-carrier---preceding duration of contact---usually from about 0.05 hour to about 24 hours period, for example, from about 0.05 hour to about 2 hours.Also can use from about 10 minutes to about 60 minutes preceding duration of contact.

Alternatively, carry out preceding contact process in a plurality of steps rather than in single stage, prepare a plurality of mixtures therein, each comprises not catalyst component on the same group.For example, contact at least two kinds of catalyst components and form first mixture, then contact first mixture and at least a other catalyst component, form second mixture, etc.

Contact procedure can be carried out in single container or in a plurality of container before a plurality of.Further, before a plurality of contact procedures continuously (or sequentially), abreast or its carry out in combination.For example, first mixture of two kinds of catalyst components can form in first container, comprise that first mixture adds that second mixture of another catalyst component can form in first container or second container, second container typically is placed on the downstream of first container.

On the other hand, one or more catalyst components can separate and use different preceding the contacts in the processing.For example, the part of catalyst component is added the first preceding contacting container, with with at least a other catalyst component before contact, and the remainder of same catalyst component is added the second preceding contacting container, with with at least a other catalyst component before contact, or directly add in the reactor, or its combination.Before contact can in suitable equipment, carry out, for example bucket, mix bucket, various static mixing device, flask, the container of any type or the combination of these devices.

In another aspect of this invention, when polyreaction was carried out, various catalyst components (for example, bridged combined metal, activator-carrier, organoaluminum promotor with randomly unsaturated hydrocarbons) contacted in polymerization reactor simultaneously.Alternatively, arbitrarily two or more these catalyst components can be before entering reaction zone in container before contact.Contact procedure can be continuous before this, wherein before product of contact be added in the reactor continuously, or it can be substep or batchwise process, wherein a collection of before product of contact be added into to prepare catalyst composition.Before this contact procedure can scope can be from several seconds to as many as a couple of days or even the longer period carry out.In this respect, continuous preceding contact procedure generally continues about 1 second to about 1 hour.On the other hand, continuous preceding contact procedure continues about 10 seconds to about 45 minutes or about 1 minute to about 30 minutes.

In case the pre-contact mixture of metallocene compound, olefinic monomer and organoaluminum promotor contacts with activator-carrier, said composition (having added activator-carrier) is called as " back contact mixture ".Before the beginning polymerization process, randomly, can make described back contact mixture keep in touch for second period, i.e. back duration of contact.Between pre-contact mixture and activator-carrier back duration of contact scope generally at about 0.05 hour to about 24 hours.On the other hand, back duration of contact was at about 0.05 hour to about 1 hour.With do not have contact in advance or back contact and the same catalyst composition of preparation is compared, pre-contact, after contact procedure or the two can increase the productivity of polymkeric substance.Yet pre-contact procedure and back contact procedure are all optional.

Back contact mixture can be heated under a temperature, and the time be enough to make pre-contact mixture and activator-carrier to adsorb, flood or interact so that a part of component of pre-contact mixture is fixed, adsorbs or deposits thereon.When adopting heating, back contact mixture heats to the temperature between about 150 ℉ at about 0 ℉ usually, and for example, about 40 ℉ are to about 95 ℉.

According to an aspect of of the present present invention, the mol ratio of the mole number of the mole number of metallocene compound and organo-aluminium compound is generally from about 1:1 to about 1:10 in the catalyst composition, 000 scope.On the other hand, mol ratio be from about 1:1 to about 1:1,000 scope.More on the other hand, the mol ratio of the mole number of the mole number of metallocene compound and organo-aluminium compound is the scope from about 1:1 to about 1:1:100.If contact and/or back contact procedure before using, before these mol ratios reflections contact mixture and back contact mixture in conjunction with in metallocene compound or the ratio of the total amount of the total mole number of multiple metallocene compound and organo-aluminium compound (or multiple organo-aluminium compound).

Before using during contact procedure, the mol ratio of the total mole number of the total mole number of olefinic monomer and metallocene compound typically is from about 1:10 to about 100 in the preceding contact mixture, the scope of 000:1.Use the total mole number of each composition that of the present invention wherein the use more than a kind of olefinic monomer and/or more than a kind of aspect of metallocene compound is described with this ratio.Further, in another aspect of the present invention, this mol ratio can be from about 10:1 to about 1, the scope of 000:1.

Generally speaking, the weight ratio of organo-aluminium compound and activator-carrier be from about 10:1 to about 1:1000 scope.If use more than a kind of organo-aluminium compound and/or more than a kind of activator-carrier, this ratio is based on each gross weight of composition separately.On the other hand, the weight ratio of organo-aluminium compound and activator-carrier is to about 1:50 scope from about 3:1 to about 1:100 or from about 1:1.

Aspect more of the present invention, the weight ratio scope of metallocene and activator-carrier is to about 1:1,000,000 from about 1:1.If use more than a kind of metallocene and/or more than a kind of activator-carrier, this ratio is based on each gross weight of composition separately.On the other hand, this weight ratio be from about 1:5 to about 1:100,000 scope, or from about 1:10 to about 1:10,000 scope.More on the other hand, the weight ratio of metallocene compound and activator-carrier is the scope from about 1:20 to about 1:1000.

According to aspects more of the present invention, do not need aluminium alkoxide compound to form catalyst composition.Therefore, under the situation that does not have aikyiaiurnirsoxan beta, carry out polymerization.Therefore, the present invention can use for example organo-aluminium compound and activator-carrier under the situation that does not have aikyiaiurnirsoxan beta.Though be not intended to be retrained by theory, believe that organo-aluminium compound may not activate metallocene catalyst in the mode identical with the Organoaluminoxy hydride compounds.

In addition, in some aspects, form catalyst composition of the present invention without the need for machine boron and organic boronic salt compound.Even so, aikyiaiurnirsoxan beta, organic boron or organic boronic salt compound, ionizing ionic compound or its combination can be used being considered and being included in other catalyst composition in the present invention.Therefore, can use aikyiaiurnirsoxan beta, organic boron or organic boronic salt compound, ionizing ionic compound or its combination with metallocene compound, for example, under organo-aluminium compound existence or non-existent situation.

Catalyst composition of the present invention generally has every gram activator-carrier per hour greater than the catalyst activity (abbreviation gPE/ (gAShr)) of about 100 gram polyethylene (homopolymer, multipolymer etc., based on context require).On the other hand, catalyst activity greater than about 150, greater than about 200 or greater than about 250gPE/ (gAShr).More on the other hand, catalyst composition of the present invention with have greater than about 500, greater than about 1000 or be feature greater than the about catalyst activity of 1500gPE/ (gAShr).More on the other hand, catalyst activity is greater than about 2000gPE/ (gAShr).This activity be under slurry polymerization conditions, use Trimethylmethane as thinner, about 90 ° of C polymerization temperatures and approximately the reactor pressure of 450psig measure.

As above discuss, in aspects more of the present invention, can contact the arbitrary combination of metallocene compound, activator-carrier, organo-aluminium compound and olefinic monomer in the past.When any preceding contact took place with olefinic monomer, it is identical with the alkene of wanting copolymerization that the olefinic monomer that uses in the preceding contact procedure there is no need.Further, when the preceding contact procedure between the arbitrary combination of catalyst component carried out for first period, this preceding contact mixture can use for second period in the back contact procedure subsequently between any other combination of catalyst component.For example, can in preceding contact procedure, use metallocene compound, organo-aluminium compound and first period of 1-hexene, should preceding contact mixture can contact with activator-carrier subsequently, be formed on the back contact mixture that the beginning polyreaction contacted for second period before.For example, first period that contacts between the arbitrary combination of metallocene compound, olefinic monomer, activator-carrier and organo-aluminium compound---preceding duration of contact---can be for from about 0.05 hour to about 24 hours, from about 0.05 hour to about 1 hour or from about 10 minutes to about 30 minutes.Back contact mixture was randomly allowing to keep in touch second period before the beginning polymerization process---back duration of contact.According to an aspect of of the present present invention, the back duration of contact between preceding contact mixture and any remaining catalyst component is from about 0.05 hour to about 24 hours or from about 0.1 hour to about 1 hour.

Polymerization process

Catalyst composition of the present invention can be used for olefin polymerization, forms copolymer, terpolymer etc.Under there is situation in catalyst composition, a kind of such method that is used for olefin polymerization comprises makes catalyst composition contact under polymerizing condition with at least a olefin comonomer with olefinic monomer, produce olefin polymer, wherein catalyst composition comprises the product of contact of at least a metallocene compound and at least a activator.This polymerization process carries out in the presence of hydrogen, and generates the olefin polymer of the Mw/Mn ratio with scope from about 3 to about 6.At least a metallocene compound that uses in the catalyst composition has following formula:

Wherein:

M ¹Be Ti, Zr or Hf;

E is C or Si;

R ⁴It is the alkyl or alkenyl group with 10 carbon atoms of as many as; With

R ^5AAnd R ^5BBe H or the hydrocarbyl group with 12 carbon atoms of as many as independently; And

Olefine polymerizing process disclosed herein can use various types of polymerization reactors to carry out.As used herein, " polymerization reactor " comprise can polymerization of olefin monomers and comonomer (a kind of or more than a kind of comonomer) to produce any polymerization reactor of copolymer, terpolymer etc.Various types of reactors comprise those reactors that can be called batch reactor, slurry-phase reactor, Gas-phase reactor, solution reactor, high-pressure reactor, tubular reactor or autoclave reactor.Gas-phase reactor can comprise fluidized-bed reactor or multistage horizontal reactor.Slurry-phase reactor can comprise horizontal or vertical loop.High-pressure reactor can comprise autoclave or tubular reactor.Type of reactor can comprise intermittently or successive processes.Successive processes can be used intermittently or continuous product is discharged.Process also can comprise the partly or entirely directly circulation of unreacted monomer, unreacted comonomer and/or thinner.

Polymerization reactor system of the present invention can be included in one type reactor in the system, maybe can comprise the reactor of a plurality of identical or different types.The generation of polymkeric substance can be included in by several stages in interconnected two polymerization reactors that separate of transfer device at least in a plurality of reactors, and making the polymkeric substance that shifts the generation of first polymerization reactor enter second reactor becomes possibility.The polymerizing condition of expectation can be different with the operational condition in other reactor in one of reactor.Alternatively, in a plurality of reactors polymerization can comprise manual transfer polymerization thing from a reactor to the subsequent reaction device, so that successive polymerization.A plurality of reactor assemblies can include but not limited to following arbitrary combination: the combination of the combination of a plurality of loop reactors, a plurality of Gas-phase reactor, loop and Gas-phase reactor, a plurality of high-pressure reactor or high-pressure reactor and loop and/or Gas-phase reactor.A plurality of reactors can or be operated abreast with series connection.

According to an aspect of of the present present invention, polymerization reactor system can comprise that at least one contains the loop slurry reactor in horizontal or vertical loop.Monomer, thinner, catalyzer and comonomer can join in the loop reactor of polymerization generation continuously.Generally speaking, successive processes can comprise that continuous introducing monomers/comonomers, catalyzer and thinner enter in the polymerization reactor and remove the suspension that comprises polymer beads and thinner continuously from this reactor.Can make the reactor effluent flash distillation to shift out solid polymer from the liquid that comprises thinner, monomer and/or comonomer.Various technology can be used for this separating step, and it includes but not limited to: can comprise the flash distillation of heating and decompression; Separation by the action of the whirlwind in whirlwind or wet cyclone; Or by centrifugation.

Typical slurry phase polymerisation process (being also referred to as the particle form method) is for example at United States Patent (USP) 3,248, and 179,4,501,885,5,565,175,5,575,979,6,239,235,6, open in 262,191 and 6,833,415, its each incorporate this paper by reference in full into.

The suitable thinner that uses in slurry polymerization includes but not limited to the monomer that is aggregated and is the hydrocarbon of liquid under reaction conditions.Suitably the example of thinner includes but not limited to hydrocarbon for example propane, hexanaphthene, Trimethylmethane, normal butane, Skellysolve A, iso-pentane, neopentane and normal hexane.Some loop polymerization reactions can take place under the bulk conditions of not using thinner.An example is the polymerization of propylene monomer, and as at United States Patent (USP) 5,455, open in 314, it incorporates this paper by reference in full into.

According on the other hand of the present invention, polymerization reactor can comprise at least one Gas-phase reactor.These systems can use the continuous cycling stream that contains one or more monomers that cycles through fluidized-bed under polymerizing condition in the presence of catalyzer continuously.Cycling stream can be withdrawn from also recirculation from fluidized-bed and get back to reactor.Simultaneously, polymer product can be withdrawn from the monomer that can add to replace polymerization with new or fresh monomer from reactor.These Gas-phase reactor can comprise the multistep gas-phase polymerization processes of alkene, in this process alkene at least two independently in the vapour phase polymerization district with vapour phase polymerization, be added in the polymkeric substance that contains catalyzer that forms in first polymeric area simultaneously to second polymeric area.One type Gas-phase reactor is at United States Patent (USP) 5,352, and open in 749,4,588,790 and 5,436,304, each in them is incorporated this paper by reference in full into.

According to of the present invention also on the other hand, pressure polymerization reactor can comprise tubular reactor or autoclave reactor.Tubular reactor can have several districts that add new monomer, initiator or catalyzer therein.Monomer can be entrained in the inert gas and in a district of reactor and introduce.Initiator, catalyzer and/or catalyst component can be entrained in the air-flow and in another district of reactor and introduce.Can mixed airflow, be used for polymerization.Suitably use heat and pressure to obtain optimum polymeric reaction condition.

According on the other hand of the present invention, polymerization reactor can comprise solution polymerization reactor, and wherein monomers/comonomers contacts by agitation as appropriate or alternate manner with catalyzer.Can use the carrier that comprises inertia organic thinner or excess monomer.If desired, under fluent material existence or non-existent situation, monomers/comonomers can be introduced in the gas phase contacting with the catalyst reaction product.Polymeric area maintains the temperature and pressure that can cause that polymers soln forms in reaction medium.Can use stirring to control and keep the polyblend of homogeneous to obtain better temperature at whole polymeric area.Utilize appropriate means, be used for diffuse-aggregate heat release.

Be suitable for polymerization reactor of the present invention and can also comprise at least a raw material supplying system, at least a catalyzer or the plenum system of catalyst component and/or the arbitrary combination of at least a polymer recovery system.Be used for appropriate reaction device of the present invention system can also comprise for feed purification, catalyzer store and prepare, extrude, the system of reactor cooling, polymer recovery, classification, circulation, storage, unloading (loadout), lab analysis and process control.

The condition of controlling with the expectation polymer property is provided for polymerization efficiency comprises temperature, pressure and various concentration of reactants.Polymerization temperature can influence catalyst production, polymericular weight and molecular weight distribution.Suitable polymerization temperature can be according to the arbitrary temp of Ji Busen free energy equation below the depolymerization temperature.Typically, depend on the type of polymerization reactor, this comprises about 60 ° of C to about 280 ° of C, for example, or from about 60 ° of C to about 110 ° of C.In some reactor assemblies, polymerization temperature generally is from about 70 ° of C to about 90 ° of C or the scope from about 75 ° of C to about 85 ° of C.

Suitable pressure also can change according to reactor and polymeric type.Be used for the pressure of loop reactor liquid polymerization typically less than 1000psig.Be used for the pressure of vapour phase polymerization usually about 200 to 500psig.High pressure polymerisation in tubular type or the autoclave reactor generally carries out about 20,000 to 75,000psig.Operate in the supercritical region that polymerization reactor also can occur under higher usually temperature and pressure.The above operation of the stagnation point of Pressure/Temperature figure (supercritical phase) can provide advantage.

According to an aspect of of the present present invention, the ratio of hydrogen and olefinic monomer is controlled in the polymerization process.Based on the weight of olefinic monomer, this weight ratio can be from 50ppm to about 10, the hydrogen of 000ppm.For example, the reactant of hydrogen and olefinic monomer or charge ratio can be controlled in and fall into about 50ppm to about 7500ppm, from about 50ppm to about 5000ppm or the weight ratio in from about 50ppm to about 1000ppm scope.In addition, in aspect more of the present invention, the reactant of hydrogen and olefinic monomer or charge ratio can be controlled in from about 75ppm to about 900ppm, from about 100ppm to about 800ppm or the weight ratio the scope from about 125ppm to about 700ppm.

In the ethylene polymerization, no matter the comonomer (one or more) that uses how, the charge ratio of hydrogen and vinyl monomer is generally controlled the weight ratio in from about 50ppm to about 1000ppm scope, but concrete weight ratio target can be according to polymericular weight or the melt index (MI) of expectation.Ethene polymers (copolymer, terpolymer etc.) for the MI with about 1g/10min, the weight ratio of hydrogen and ethene typically is from about 50ppm to about 250ppm, for example, such as from about 75ppm to about 225ppm or from about 100ppm to about 200ppm.When high-melt index more, about 75-125g/10min for example, this hydrogen: ethylene feed is than normally from about 400ppm to about 1000ppm or from about scope of 500 to about 900ppm.

On the other hand, during polymerization was carried out, hydrogen was more constant than keeping substantially with charge ratio or the reactant of olefinic monomer, to obtain specific polymerization-grade.Just, hydrogen: the alkene ratio is chosen in from about 50ppm to about 10, the specified proportion in the 000ppm scope, and during polymerization is carried out, keep this ratio within approximately+/-25%.For example, if target proportion is 100ppm, keep hydrogen so: the basicly stable meeting of olefin ratios makes charge ratio remain on about 75ppm between about 125ppm.Further, during whole polymerization was carried out, the adding of comonomer (or multiple comonomer) can be and generally be basicly stable, to obtain specific polymerization-grade.Reactant used herein/charging strategy is different from the pulse (pulsing) that for example United States Patent (USP) 5,739,220 and United States Patent (USP) disclose the reactant that uses in 2004/0059070.

More on the other hand, the discharge flush gas from polymerization reactor disclosed herein (effluent flush gas) generally has less than about 0.01 hydrogen and the mol ratio of olefinic monomer, though this ratio can depend on polymericular weight, MI of expectation etc.In the vinyl polymerization, hydrogen: the mol ratio of ethene typically is less than about 0.01, and usually less than about 0.005.For example, for the ethylene copolymer with 150g/10min high load melt index (HLMI), discharge this hydrogen in the flush gas: ethylene molar ratio is generally less than about 0.005.

Aspect some, polymerization process disclosed herein can be carried out in single reactor of the present invention.Therefore, do not require a plurality of reactor assemblies.Olefin polymer (for example, ethylene copolymer) can produce in single reactor in the presence of hydrogen and Metallocenyl catalyst system, generates to have from about 3 polymkeric substance to about 6 scope Mw/Mn ratios.Further, single reactor can be for example Gas-phase reactor as discussed above, loop reactor or agitator tank reactor.

Can control the reactant concn that enters polymerization reactor has some physics and mechanical properties with generation resin.The suggestion end-use product that forms by fluoropolymer resin and the method that forms the sort of product finally can be determined polymer property and the attribute expected.Mechanical properties comprises stretching, deflection, impact, creep, stress relaxation and hardness test.Physical properties comprises melt temperature (temperature melt of crystallization), density, stereoregular (stereoregularity), crack growth, long chain branching and the flow measurement (rheologicalmeasurements) of density, molecular weight, molecular weight distribution, melting temperature (Tm), second-order transition temperature, crystallization.

The present invention also relates to the polymkeric substance by any polymerization process generation disclosed herein.Concrete polymer property and feature discuss in more detail in a lower section.The object of making can also can comprise the polymkeric substance that produces according to the present invention from the polymer formation that produces according to the present invention.

Polymkeric substance and object

If the generation polymkeric substance that produces according to the present invention for example is polymkeric substance or the multipolymer of ethene, its character can characterize by various analytical technologies known and that use in polyolefin industry.The object of making can form from ethene polymers of the present invention, and can comprise ethene polymers of the present invention, and its typical character provides following.

The ethene polymers (copolymer, terpolymer etc.) that produces according to the present invention generally has from about melt index of 0.01 to about 100g/10min.Aspects more of the present invention are considered about 0.1 to about 50g/10min or from about 0.3 melt index to about 20g/10min scope.For example, polymkeric substance of the present invention can have from about 0.5 to about 10, from about 0.5 to about 6 or from about 0.5 melt index to about 3g/10min scope.

Use the density of the vinyl polymer of one or more metallocene compounds generations disclosed herein typically to fall into from about 0.88 to about 0.97g/cm ³In the scope.An aspect of of the present present invention, polyvinyl density from about 0.90 to about 0.95g/cm ³Scope in.More on the other hand, density be from about 0.91 to about 0.94g/cm ³Scope in, for example, such as, from about 0.91 to about 0.93g/cm ³

Have from about 15,000 to about 350, for example copolymer and terpolymer be within the scope of the invention for the ethene polymers of the weight-average molecular weight (Mw) in the 000g/mol scope.Usually, the Mw of polymkeric substance of the present invention is from about 20,000 to about 250, in the 000g/mol scope, for example, and from about 50,000 to about 200,000g/mol or from about 70,000 to about 150,000g/mol.

A kind of the measuring of polyvinyl molecular weight distribution disclosed herein is polydispersity index or Mw/Mn ratio, and wherein Mw is that weight-average molecular weight and Mn are number-average molecular weights.Generally speaking, the Mw/Mn by polymkeric substance traditional rather than metallocene catalyst systems produce of the present invention than from about 2.0 to about 2.5 scopes.Yet, the Mw/Mn of polymkeric substance of the present invention than from about 3 to about 6 scope.Some aspects, polymkeric substance Mw/Mn than from about 3.1 to about 5.5 or from about 3.1 to about 5.0 scope.In other side, the Mw/Mn of polymkeric substance from about 3.2 to about 4.8, from about 3.2 to about 4.5, from about 3.3 to about 4.4 or from about 3.5 to about 4.4 scope.

The ethene polymers that uses polymerization process described above and catalyst system to produce has anti-copolymerization monomer distribution.As using in this article, anti-copolymerization monomer distribution refers to therein that the higher molecular weight component comparison low molecular weight compositions of polymkeric substance has the polymkeric substance that higher comonomer mixes.Generally speaking, along with the increase of molecular weight, comonomer mixes increase.Usually, the amount of mixing at the comonomer of higher molecular weight than lower molecular weight high about 20% or high by 30%.On the one hand, the amount of mixing at the comonomer of higher molecular weight is than at high about 50% of lower molecular weight.The another one feature of anti-copolymerization monomer distribution be the quantity of short chain branch (SCB) of per 1000 total carbon atoms at the Mw place greater than at the Mn place.

The short chain branch distribution (SCBD) of polymkeric substance of the present invention also can be passed through 10 ^5.5The SCB quantity of per 1000 the total carbon atoms of the polymkeric substance of molecular weight with 10 ⁴The ratio of the SCB quantity of per 1000 the total carbon atoms of the polymkeric substance of molecular weight is namely (10 ^5.5The SCB of molecular weight)/(10 ⁴The SCB of molecular weight) characterizes.Among the present invention, this ratio is greater than 1.On the other hand, 10 ^5.5The SCB quantity of per 1000 the total carbon atoms of the polymkeric substance of molecular weight with 10 ⁴The ratio of the SCB quantity of per 1000 the total carbon atoms of the polymkeric substance of molecular weight is greater than about 1.2, for example greater than about 1.3.In the other side, this ratio is greater than about 1.5.More on the other hand, this ratio from about 1 to about 5, from about 1.2 to about 4 or from about 1.3 to about 3.5 scope.As an example, 10 ^5.5The SCB quantity of per 1000 the total carbon atoms of the polymkeric substance of molecular weight with 10 ⁴The ratio of the SCB quantity of per 1000 the total carbon atoms of the polymkeric substance of molecular weight can from about 1.5 to about 3 scope.

In addition, the SCBD of polymkeric substance of the present invention can be by at the SCB quantity of per 1000 the total carbon atoms of the polymkeric substance of D90 and SCB quantity ratio at per 1000 the total carbon atoms of the polymkeric substance of D10, i.e. (at the SCB of D90)/(at the SCB of D10) characterizes.Molecular weight when D90 is by weight and calculates 90% polymkeric substance and have higher molecular weight, and D10 is by weight the molecular weight when calculating 10% polymkeric substance and having higher molecular weight.D90 and D10 have been described in diagram among Fig. 2.According to an aspect of of the present present invention, short chain branch (SCB) quantity of per 1000 the total carbon atoms of the polymkeric substance of D90 with in the ratio of the SCB quantity of per 1000 the total carbon atoms of the polymkeric substance of D10 less than about 0.9.For example, (at the SCB of D90)/(at the SCB of D10) ratio can from about 0.1 to about 0.9 scope.On the other hand, this ratio is less than about 0.8 or less than about 0.7.More on the other hand, be from about 0.2 to about 0.8 scope in the SCB quantity of per 1000 the total carbon atoms of the polymkeric substance of D90 and ratio in the SCB quantity of per 1000 the total carbon atoms of the polymkeric substance of D10, for example, such as, from about 0.3 to about 0.7.

Analysis temperature rising elution fractionation (ATREF) can be used for characterizing the SCBD of the open polymkeric substance of this paper.In ATREF test, below 40 ℃ temperature, calculate by weight less than these polymkeric substance of about 5% by wash-out.On the other hand, in ATREF test, calculate by weight less than about 4% below 40 ℃ the temperature or calculate by weight less than about 3% polymkeric substance by wash-out.For example, in the ATREF test, calculating by weight below 40 ℃ the temperature can be by wash-out less than about 1% polymkeric substance.

Generally speaking, polymkeric substance of the present invention has low-level long chain branches, typically is to have per 1000 total carbon atoms less than about 0.05 long chain branches (LCB).In some aspects, the LCB quantity of per 1000 total carbon atoms be less than about 0.04, less than about 0.03, less than about 0.02 or less than about 0.01.In addition, in the other side of the present invention, polymkeric substance of the present invention can have per 1000 total carbon atoms less than about 0.008, less than about 0.006, less than about 0.005, less than about 0.004, less than about 0.003, less than about 0.002 or less than about 0.001 LCB.

Polyvinyl illustrative of the present invention and non-limitative example can be by following signs: from about melt index of 0.1 to about 100g/10min; From about 3 to about 6 Mw/Mn ratio; With anti-copolymerization monomer distribution.This polymkeric substance also has per 1000 total carbon atoms less than about 0.05 LCB; With in ATREF test, calculate by weight below 40 ℃ the temperature less than about 5% polymkeric substance by wash-out.

The another one exemplary ethylene polymers has: from about melt index of 0.3 to about 20g/10min; From about 3.1 to about 5.0 Mw/Mn ratio; Anti-copolymerization monomer distribution; Per 1000 total carbon atoms are less than about 0.01 LCB; With in ATREF test, calculate by weight below 40 ℃ the temperature less than about 3% polymkeric substance by wash-out.

More another ethene polymers disclosed herein has: from about melt index of 0.5 to about 10g/10min; From about 3.2 to about 4.5 Mw/Mn ratio; Anti-copolymerization monomer distribution; Per 1000 total carbon atoms are less than about 0.005 LCB; With in ATREF test, calculate by weight below 40 ℃ the temperature less than about 1% polymkeric substance by wash-out.

Can form the object of various manufacturings regardless of the ethene polymers that is copolymer, terpolymer etc.The object that can comprise polymkeric substance of the present invention includes but not limited to agricultural film, auto parts, bottle, bucket, fiber or fabric, food product packing film or container, food object, tanks, geomembrane, household receptacle, liner, moulded product, medicine equipment or material, pipeline, plate or band, toy etc.Can make ins all sorts of ways forms these objects.The non-limitative example of these methods comprises that injection moulding, blowing, rotoforming, film are extruded, sheet material is extruded, section bar is extruded, thermoforming etc.In addition, add additive and properties-correcting agent usually in these polymkeric substance, so that favourable polymer processing attribute or end-use product attribute to be provided.

Embodiment

The present invention illustrates further that by following embodiment they should not be interpreted as scope of the present invention is applied restriction by any way.After reading the specification sheets of this paper, do not departing under the scope situation of spirit of the present invention or claims, various other sides, embodiment, modification and its are equal to can make those skilled in the art expect.

(MI g/10min) measures with 2,160 gram weight at 190 ° of C according to ASTM D1238 melt index.

(HLMI g/10min) measures with 21,600 gram weight at 190 ° of C according to ASTM D1238 high load melt index.

Density polymer is according to ASTM D1505 and ASTM D1928 method C, on compression molded sample, adapt to about grams (g/cm3) that was determined as every cubic centimetre in 40 hours with about 15 ° of C cooling per hour with in room temperature.

The melt rheology characterizes following carrying out.At Rheometrics Scientific, on the Inc.ARES rheometer, use parallel-plate geometry, carry out small strain (10%) oscillatory shear and measure.All rheological tests are all carried out under 190 ℃.Use three parameters C arreau-Yasuda (CY) empirical models of revising then, the fitting of a curve complex viscosity | η ^*| to frequency (ω) data, to obtain zero-shear viscosity-η ₀, feature viscosity time of relaxation-τ _ηAnd width parameter-a.Carreau-Yasuda (CY) empirical model of simplifying is as follows:

| η^{*} (ω) | = \frac{η_{0}}{{[1 + {(τηω)}^{a}]}^{(1 - n) / a}},

Wherein: | η ^*(ω) | the modulus of=plural shear viscosity;

η ₀=zero-shear viscosity

τ _η=viscosity time of relaxation

A=" width " parameter

N=fixes final power law slope, is fixed on 2/11; With

The radian frequency of ω=oscillatory shear deformation.

Can be found in the meaning of CY model and derived parameter and the details of explanation: C.A.Hieber and H.H.Chiang, Rheol.Acta, 28,321 (1989); C.A.Hieber and H.H.Chiang, Polym.Eng.Sci., 32,931 (1992); And R.B.Bird, R.C.Armstrong and O.Hasseger, Dynamics of Polymeric Liquids, Volume1, Fluid Mechanics, 2nd Edition, John Wiley﹠amp; Sons (1987), its each all introduced by reference at this.

Adopt PL220SEC high temperature chromatogram unit (Polymer Laboratories), obtain molecular weight and molecular weight distribution, wherein using trichlorobenzene (TCB) is solvent, and flow velocity is 1mL/min, and temperature is 145 ℃.Working concentration is the BHT(2 of 0.5g/L, 6-two-tertiary butyl-4-methylphenol) as the stablizer among the TCB.Adopt the injection volume of 200 μ L, nominal polymer concentration is 1.5mg/mL.By heating 5 hours down at 150 ℃, carry out mild stirring sometimes, carry out the dissolving of sample in stable TCB.Used pillar is three PLgel Mixed A LS posts (7.8 * 300mm), and with the determined wide linear polyethylene standard (Phillips of molecular weight

BHB5003) calibrate.

Use as by P.J.DesLauriers, D.C.Rohlfing and E.T.Hsieh, Polymer, the SEC-FTIR heat flow cells of describing in 43,159 (2002) (flow cell) (Polymer Laboratories) obtain the SCBD data.The ATREF step is as follows: 1,2 of 40 milligrams polymer samples and 20mL, 4-trichlorobenzene sequentially are added in the container on the PolyChar TREF200+ instrument.After the polymer dissolution, the aliquots containig of polymers soln is loaded on the post and with 0.5 ° of C/min and is cooled to 35 ° of C.Subsequently, bring into use 0.5mL/min flow velocity wash-out and reach 120 ° of C with 1 ° of C/min heating.

Sulfated alumina activator-the carrier that uses in some samples is prepared according to following steps.Obtaining name from W.R.Grace Company company is called " Alumina A " and has about 300m ²The boehmite (Bohemite) of the surface-area of/g and about 1.3mL/g pore volume.This material obtains as the powder with about 100 microns mean particle size.It is wetting to beginning to flood this material with ammonium sulfate solution, to equaling about 15% vitriol.Place this mixture subsequently in the square position and be allowed to condition at about 16 hours of about 110 ° of C vacuum-dryings.

For calcinated support, this powdered mixture of about 10 grams is placed in 1.75 inches silica tubes of bottom assembling sintered quartz dish.When powder is supported on dish when going up, the air (nitrogen can be replaced) by passing 13X molecular sieve column drying upwards with about 1.6 to 1.8 standard cubic foots/hour linear velocity blow over dish.600 ° of C calcining temperatures of expectation are opened and be warmed up to the speed of about 400 ° of C per hour to electric furnace around the silica tube subsequently.In this temperature, allow about 3 hours of powder fluidisation in dry air.Then, collection sulfated alumina activator-carrier is also stored under the drying nitrogen condition, and use under the situation that is not exposed to atmosphere.

Comparing embodiment 1-2

The polymkeric substance that uses the chromium-based catalysts system to produce

Produce comparing embodiment 1-2 according to following steps.The name that obtains from W.R.Grace is called chromium/SiO 2 catalyst of 969MPI by the activation in 3 hours of calcining 700 ° of C fluidized-beds.Under nitrogen, add about 0.1g then to being equipped with in temperature control and the 2.2-L autoclave with the paddle stirrer of 400rpm running.The Trimethylmethane liquid that adds about 1.2L adds hydrogen (if you are using) subsequently.Hydrogen is stored gas cylinder at 25 ° of C from the 1L supercharging and is added reactor.Add enough hydrogen, in storing gas cylinder, to cause the pressure drop of 100psig.The temperature of reactor is elevated to 103 ° of C subsequently.Ethene is added to 550psig, and between polymerization period, adds to keep pressure continuously.Therefore, exist or do not exist under the situation at hydrogen, carry out polymerization at the pressure of 103 ° of C temperature, 550psig.Stop polymerization by emptying after about 60 minutes.

Fig. 3 has compared the molecular weight distribution of comparing embodiment 1-2 polymkeric substance, and Table I is listed Mw, Mn and Mw/Mn compares, the measurement of molecular weight distribution.The result of comparing embodiment 1-2 shows that the adding of hydrogen produces the polymkeric substance that has than narrow molecular weight distributions in vinyl polymerization.

Table I. the polymer property of comparing embodiment 1-2

Embodiment 3-7

The polymkeric substance that uses metallocene MET1 to produce

The aggregation test of embodiment 3-7 is following carrying out in 1 gallon of (3.8 liters) stainless steel reactor.At first, reactor also cleans with Trimethylmethane steam subsequently with nitrogen.In rejection butane steam, approximately the MET1 of sulfated alumina activator-carrier of the 1M TIBA of 0.5mL or TNBA organoaluminum promotor, 100mg and 0.5mg or 0.68mg adds in this order through charging opening.MET1 is added by the 1mg/mL solution by dissolving 20mg metallocene-prepared in 20mL toluene.The Trimethylmethane of 1.8L is closed and added to charging opening.The contained thing of stirred reactor also is heated to 80 ° of C.The 1-hexene of 30 grams adds reactor subsequently, then introduces ethene and hydrogen, adds hydrogen with respect to ethylene stream with the fixed mass ratio.Hydrogen is stored in the pressurized vessel of 340mL and through automatic feed system and adds with ethene, and the adding of the ethene/hydrogen by associating is kept whole reactor pressure at 340psig simultaneously.At last, the total amount of adding hydrogen is recorded as the pressure drop in the 340mL container.Contained thing in the reactor maintains operating temperature 19 or 30 minutes by automatization heating-cooling system.The character of the polymkeric substance condition of embodiment of the invention 3-6 and comparing embodiment 7 and generation polymkeric substance is listed in Table II.

The molecular weight distribution of the polymkeric substance of Fig. 4 comparing embodiment 3-7, and Table II is listed the measurement of MI, HLMI, density, Mw, Mn and Mw/Mn ratio, molecular weight distribution.As by as shown in the result of comparing embodiment 3-6 and embodiment 7, exist the polymkeric substance that uses the MET1 generation under the situation than not existing the polymkeric substance that produces under the situation to have wider molecular weight distribution at hydrogen at hydrogen.

Table II. the polymerizing condition of embodiment 3-7 and polymer property

Table II (continuing)

Embodiment 8-14

The polymkeric substance that uses MET I or MET2 to produce

The aggregation test of embodiment 8-14 is following carrying out in the stainless steel reactor of 1 gallon (3.8 liters).At first, reactor is with nitrogen and use the Trimethylmethane steam flushing subsequently.Approximately the MET1 of sulfated alumina (SA) activator-carrier of the TIBA organoaluminum promotor of the 1M of 0.5mL, 100mg and specified amount or MET2 add in this order by charging opening in rejection butane steam.1mg/mL solution by the metallocene-prepared of dissolving 20mg in the toluene of 20mL adds MET1 or MET2.The Trimethylmethane of 2L is closed and added subsequently to charging opening.The contained thing of stirred reactor also is heated to 80 ° of C.During aggregation test, use automatization heating-cooling system, keep contained thing in that temperature.Add comonomer 1-hexene subsequently in reactor, introduce ethene and hydrogen by automatic feed system with the fixed mass ratio subsequently.During whole test, keep whole reactor pressure at 355psig by the automatization feed system.Ethene and hydrogen are introduced on demand, to keep the 355psi total pressure of expectation in 30 minutes aggregation test.The character of the polymerizing condition of embodiment of the invention 8-11 and comparing embodiment 12-14 and generation polymkeric substance is listed in Table III.

The molecular weight distribution of the polymkeric substance of Fig. 5 comparing embodiment 8-14, and Table III is listed the measurement of MI, HLMI, density, Mw, Mn and Mw/Mn ratio, molecular weight distribution.As by as shown in the result of comparing embodiment 8-11 and embodiment 12, exist the polymkeric substance that uses the MET1 generation under the situation than not existing the polymkeric substance that produces under the situation to have wider molecular weight distribution at hydrogen at hydrogen.MET1 is than MET2---having hydrogen---also produces polymkeric substance than wide molecular weight distribution, as showing by comparing embodiment 8-11 (MET1) and embodiment 13-14 (MET2) in Fig. 5 and Table III.

The SCBD that in Fig. 6, has compared embodiment 9 and 12.Embodiment 9 exists under the situation at hydrogen and uses MET1 to produce and have anti-copolymerization monomer distribution.As showing in Fig. 6, the SCB quantity of per 1000 total carbon atoms of embodiment 9 is big at Mn at the Mw ratio.Further, 10 ^5.5The SCB quantity of per 1000 total carbon atoms of molecular weight with 10 ⁴The ratio of the SCB quantity of per 1000 total carbon atoms of molecular weight is greater than 1.

Table III. polymkeric substance condition and the polymer property of embodiment 8-14

Table III (continuing)

Embodiment 15-28

The polymkeric substance that uses metallocene MET1, MET2 or MET3 to produce

The aggregation test of embodiment 15-28 is following carrying out in loop reactor.Use 27.3 gallons (103.3 liters) or 31.2 gallons of (118 liters) slurry loop reactor as polymerization reactor.In loop reactor, continuously carry out aggregation test under the process condition (being also referred to as the slurry process) of particle form, be by 500 or the agitated autoclave of 1000mL in make the 1-hexene solution of metallocene contact with sulfated alumina activator-carrier also to output to continuously in the loop reactor with triisobutyl aluminium (TIBA) to carry out.

Carry out preceding contact in following mode.The 1-hexene solution of the Trimethylmethane solution of TIBA and metallocene adds the menifold upstream of solid activating agent feeder outlet as the stream that separates, therein they contact with each other and with isobutane flush (flush) combination.Solution flushing solid activating agent with associating enters autoclave, just contacts the TIBA/ metallocene before entering autoclave momently.The associating rinse solution that enters autoclave for the transportation solid activating agent is set in the autoclave meeting speed of about 20-30 minute the residence time of generation, controls by adjusting the Trimethylmethane flow velocity.Total stream from autoclave enters in the loop reactor subsequently.

The ethene that uses is polymer grade ethylene (obtaining from AirGas Specialty Gases), and it activates by A201 alumina column purifying and in 343 ° of C nitrogen.The 1-hexene that uses is polymerization-grade 1-hexene (obtaining from Chevron Phillips Chemical Company), and it is by distilling further purifying and passing AZ300 post, aluminum oxide mixed molecular sieve mixture subsequently and activate in 343 ° of C nitrogen.Loop reactor is loop reactors liquid, 15.2 cm diameters that are full of with 27.3 gallons (103.3 liters) or 31.2 gallons of (118 liters) volumes.Use liquid isobutane as thinner.Add molecular weight and the molecular distribution of hydrogen to influence polymerisate.Trimethylmethane is polymerization-grade Trimethylmethane (obtaining from Enterprise Products), and it is further by distillation purifying with pass the 13X molecular sieve column subsequently and activate in 343 ° of C nitrogen.

Reactor pressure is approximately 590psig.The temperature of reaction of using is listed in Table IV.In addition, the operant response device makes and has about 1.1 hours residence time.By 0.35mL circulate spherical non-return feeder (for example 28, feeder is 0.90mL) add solid activating agent and be added to as described above 500 or the autoclave of 1000mL in.In the reactor in about 1,000,000/0.9-4.7 (ppm) scope of metallocene concentration thinner in polymerization reactor.From reactor, remove polymkeric substance and reclaim at flashing chamber with the speed of 26-49lb/hr.For the smaller size smaller reactor, use the Vulcan drying machine, dry polymer under about 60-80 ° of C condition of nitrogen gas.Big reactor uses together with the cleaning post of operating in same temperature ranges stated.

The scope of TIBA concentration about 36-84ppm of thinner in polymerization reactor in the reactor is as listing in Table IV.Only about half of TIBA is added to autoclave and remainder directly is added in the reactor.In order to prevent accumulation of static electricity in the reactor, add as required with the commercial antistatics of the obtainable a small amount of of Octastat3000 (based on thinner weight, less than 5ppm).

The character of the polymerizing condition of embodiment 17-27 and comparing embodiment 15-16 and 28 and generation polymkeric substance is listed in Table IV.

The molecular weight distribution of the polymkeric substance of Fig. 7 comparing embodiment 15-20, and Table IV is listed the measurement of MI, HLMI, density, Mw, Mn and Mw/Mn ratio, molecular weight distribution.As by as shown in the result of comparing embodiment 17-20 and embodiment 15-16, use the polymkeric substance of MET1 generation than the polymkeric substance that uses MET2 to produce wider molecular weight distribution to be arranged.Similarly, the molecular weight distribution of the polymkeric substance of Fig. 8 comparing embodiment 15 and 21-25 illustrates simultaneously that also comparing use MET1 with MET2 obtains wider molecular weight distribution.

Fig. 9 shows the SCBD of embodiment 20-25.Among these embodiment each exists at hydrogen to be used the MET1 generation and has anti-copolymerization monomer distribution under the situation.As showing in Fig. 9, the SCB quantity of per 1000 total carbon atoms is big at Mn at the Mw ratio for embodiment 20-25.Similarly, 10 ^5.5The SCB quantity of per 1000 total carbon atoms of molecular weight with 10 ⁴The ratio of the SCB quantity of per 1000 total carbon atoms of molecular weight is greater than 1.

Use MET3 to produce comparing embodiment 28, and inventive embodiments 26-27 use MET1.The SCBD of the SCBD of comparing embodiment 28 and embodiment 26-27 among Figure 10.Though embodiment 28 does not show anti-copolymerization monomer distribution, embodiment 26-27 has anti-copolymerization monomer distribution, and the SCB quantity of per 1000 total carbon atoms is big at Mn at the Mw ratio therein.In addition, for embodiment 26-27,10 ^5.5The SCB quantity of per 1000 total carbon atoms of molecular weight with 10 ⁴The ratio of the SCB quantity of per 1000 total carbon atoms of molecular weight is greater than 1.

Figure 11 is log (η ₀) to the figure of log (Mw) and the low-level LCB of invention polymkeric substance of the present invention is described.Observe their zero shear viscosity η of linear tetrafluoroethylene polymer ₀And abide by power law relation between their the weight-average molecular weight Mw, and its power is in close proximity to 3.4.Work as η ₀Logarithm when the logarithm of Mw is drawn, this relation shows (linear polymer of mark among Figure 11) by the straight line of slope 3.4.Deviation from this linear polymer line generally is accepted as because the existence of LCB causes.Janzen and Colby have proposed model, and it is predicted for the function of specific LCB frequency as polymkeric substance Mw, with respect to log (η ₀) to the anticipated deviation of the linear graph of log (Mw).Referring to " Diagnosing long-chain branching in polyenes, " J.Mol.Struct.485-486,569-584 (1999), it incorporates this paper by reference in full into.Invention polymkeric substance 3-6,8-11 and 17-27 only depart from well-known 3.4 power laws " Anett line " a little, and it is as the indication (J.Phys.Chem.1980,84,649) of linear polymer.All these polymkeric substance have the LCB level below the line of the every 1E+06TC10 of an expression LCB, and it equates with 0.01 LCB of per 1000 total carbon atoms.

Analysis temperature rising elution fractionation (ATREF) figure diagram in Figure 12 of embodiment 20-26.List as diagram in Figure 12 and Table IV, only the polymkeric substance of very little weight fraction is at 40 ° of following wash-outs of C temperature.This explanation has considerably less comonomer in the very lower molecular weight mark polymkeric substance of unusual low temperature wash-out---being the 1-hexene in this case---exists.Therefore, more comonomer embeds in the more polymer heavy constituent, and this is consistent with the feature that these polymkeric substance have anti-copolymerization monomer distribution.

Table IV. the polymerizing condition of embodiment 15-28 and polymer property

Table IV (continuing)

Table IV (continuing).

Comparing embodiment 29-32

The polymkeric substance that uses the Z-type catalyst system to produce

Comparing embodiment 29-32 produces according to following step.In order to produce Z-type catalyst, level 951 silicon-dioxide that obtain from W.R.Grace activated by calcining 600 ° of C fluidized-beds in 3 hours.20.92g this calcined silica furnishing slurry in the dry heptane of 25 ° of C, 60mL subsequently.Then, the 1M dibutylmagnesium of 17.2mL joins in the slurry, is added dropwise to the liquid TiCl of 3.8mL subsequently ₄Subsequently, the decantation heptane is then used twice of heptane wash.Catalyzer is dry under 40 ° of C nitrogen.Approximately this catalyzer of 0.1g joins under nitrogen subsequently and is equipped with in temperature control chuck and the 2.2-L autoclave with the paddle stirrer of 400rpm running.Behind the Trimethylmethane liquid that adds 1.2L, add or do not add hydrogen as indication in Figure 13.Hydrogen joins in the reactor from the compression storage gas cylinder of 1-L at 25 ° of C.Temperature is elevated to 90 ° of C in the reactor, adds ethene at 550psig, and adds to keep the pressure between polymerization period continuously.Therefore, be aggregated in 90 ° of C temperature, 550psig pressure and hydrogen exist or non-existent situation under carry out.Stop polymerization by emptying after 60 minutes.

Figure 13 diagram comparing embodiment 29-32 is in the molecular weight distribution from 0 to 50psig scope hydrogen level.The presentation of results of comparing embodiment 29-32 adds hydrogen and has produced the polymkeric substance that has than narrow molecular weight distributions in the polymerization of ethene.

Claims

1. olefine polymerizing process, it comprises:

Make catalyst composition and olefinic monomer and at least a olefin comonomer contact to produce olefin polymer under polymerizing condition, wherein said catalyst composition comprises the product of contact of at least a metallocene compound and at least a activator,

Wherein said at least a metallocene compound has following formula:

(I), wherein:

M ¹Be Ti, Zr or Hf;

E is C or Si;

R ⁴It is the alkyl or alkenyl group with 10 carbon atoms of as many as; With

Wherein said polymerization process carries out in the presence of hydrogen; And described olefin polymer has from about 3 to about 6 Mw/Mn ratio.

2. method according to claim 1, wherein R ¹And R ²It is the aromatic yl group with 12 carbon atoms of as many as.

3. method according to claim 1, wherein R ^3AAnd R ^3BBe H or methyl independently.

4. method according to claim 1, wherein R ⁴It is the linear alkenyl group with 6 carbon atoms of as many as.

5. method according to claim 1, wherein R ^5AAnd R ^5BBe H or the tertiary butyl independently.

6. method according to claim 1, wherein said at least a metallocene compound is:

7. method according to claim 1, wherein said catalyst composition only comprises a kind of metallocene compound with formula (I).

8. method according to claim 1, wherein said at least a activator are at least a activator-carriers that comprises with the soild oxide of electrophilic anionic treatments, wherein:

Described soild oxide is oxide compound or its any mixture of silicon-dioxide, aluminum oxide, silica-alumina, aluminum phosphate, heteropoly tungstic acid salt, titanium dioxide, zirconium white, magnesium oxide, boron oxide or zinc oxide or its mixing; With

Described electrophilic negatively charged ion is sulfate radical, bisulfate ion, fluorine root, chlorine root, bromine root, iodine root, fluorosulfuric acid root, fluoroboric acid root, phosphate radical, hexafluorophosphoric acid root, trifluoracetic acid root, trifluoromethanesulfonic acid root, fluorine zirconate or hydrofluotitanic acid root or its arbitrary combination.

9. according to right 8 described methods, wherein said at least a activator-carrier also comprises metal or metal ion, and wherein said metal or metal ion are zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum or zirconium or its arbitrary combination.

10. method according to claim 1, wherein said at least a activator is at least a activator-carrier, and wherein said at least a activator-carrier is fluorided alumina, chlorinated aluminas, the bromination aluminum oxide, sulfated alumina, fluorinated silica-aluminum oxide, chlorodioxin silicon-aluminum oxide, the bromination silica-alumina, the sulfation silica-alumina, fluorinated silica-zirconium white, chlorodioxin silicon-zirconium white, bromination silicon-dioxide-zirconium white, sulfation silicon-dioxide-zirconium white, fluorinated silica-titanium dioxide, or fluorinated silica-coated aluminum oxide, or its arbitrary combination.

11. method according to claim 1, wherein said at least a activator are to comprise following at least a activator-carrier: clay mineral, column clay, strip off the type clay, be glued to the type that strips off clay in another oxide matrix, aluminium silicate mineral or non-layer aluminosilicate mineral or its any combination of layer silicate mineral, non-layer silicate mineral, stratiform.

12. method according to claim 1, wherein said catalyst composition also comprise at least a organo-aluminium compound with following formula:

Al(X ⁵) _m(X ⁶) ^3-m；

Wherein:

X ⁵It is alkyl;

X ⁶Be alkoxyl group or aryloxy, halogen root or hydride ion; With

M from 1 to 3, comprises 1 and 3.

13. method according to claim 12, wherein said at least a organo-aluminium compound are trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diisobutylaluminium hydride, diethyl aluminum ethylate or diethylaluminum chloride or its combination.

14. method according to claim 1, wherein said at least a activator are at least a aluminium alkoxide compound, at least a organic boron or organic boronic salt compound or at least a ionizing ionic compound or its arbitrary combination..

15. method according to claim 1, wherein the weight ratio of hydrogen and described olefinic monomer at about 50ppm to about 10, in the scope of 000ppm.

16. method according to claim 1, wherein said catalyst composition, described olefinic monomer and described at least a olefin comonomer contact in single reactor, and wherein said single reactor is Gas-phase reactor, loop reactor or agitator tank reactor.

17. method according to claim 1, wherein said olefinic monomer is ethene.

18. method according to claim 1, wherein said at least a olefin comonomer are propylene, 1-butylene, 2-butylene, 3-methyl-1-butene, iso-butylene, 1-amylene, 2-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene or vinylbenzene or its mixture.

19. method according to claim 1, wherein said olefin polymer has anti-copolymerization monomer distribution.

20. method according to claim 1, wherein said olefin polymer have per 1000 total carbon atoms less than about 0.05 LCB.

21. method according to claim 1, wherein in the following ATREF of the temperature of the 40 ° of C test less than calculating by weight about 5% described polymkeric substance by wash-out.

22. polymkeric substance, it is by the described method production of claim 1.

23. object, it comprises the polymkeric substance of producing by the described method of claim 1.